Iminothiazolines, their production and use as herbicides, and intermediates for their production

ABSTRACT

An iminothiazoline compound of the formula:  &lt;IMAGE&gt;  which is useful as a herbicide.

This application is a divisional of application Ser. No. 08/005,050,filed on Jan. 15, 1993, now U.S. Pat. No. 5,426,188 which is aDivisional of Ser. No. 07/769,485 filed Oct. 1, 1991, now U.S. Pat. No.5,244,863 which is a Continuation-In-part of Ser. No. 07/668,986 filedMar. 12, 1991, now abandoned, the entire contents of which are herebyincorporated by reference.

The present invention relates to iminothiazolines, their production anduse as herbicides, and intermediates for their production. Moreparticularly, it relates to iminothiazoline compounds having strongherbicidal potency and showing noticeable selectivity between cropplants and weeds, and intermediate compounds for production of saidiminothiazoline compounds.

Some certain iminothiazolidine derivatives are known to be useful asactive ingredients in herbicidal compositions (cf. EP-A-0349282).However, their herbicidal potency is not sufficiently high, or theirselectivity between crop plants and weeds is not always sufficient.Thus, they can hardly be said to be satisfactory herbicides.

An extensive study has been made seeking satisfactory herbicides, and asthe result, it has been found that iminothiazoline compounds of theformula: ##STR2## wherein R¹ is a halogen atom, a halogen-substituted C₁-C₂ alkyl group or a halogen-substituted C₁ -C₂ alkyloxy group, R² is amethyl group, an ethyl group, a chlorine atom, a bromine atom or aniodine atom and R³ is a formyl group, a C₁ -C₆ alkylcarbonyl group, abenzylcarbonyl group, a C₃ -C₄ alkenyloxycarbonyl group, a C₃ -C₄alkynyloxycarbonyl group, a C₁ -C₆ alkyloxycarbonyl group, a C₁ -C₆alkyloxycarbonyl group substitued with C₁ -C₂ alkyloxy or phenyl, acyclo(C₃ -C₆)alkylcarbonyl group, a cyclo(C₃ -C₆)alkylcarbonyl groupsubstituted with methyl, a cyclo(C₃ -C₆)alkyloxycarbonyl group, abenzoyl group, an N-(C₁ -C₃)alkylcarbamoyl group, a phenoxycarbonylgroup, a halogen-substituted C₁ -C₆ alkylcarbonyl group or ahalogen-substituted C₁ -C₃ alkylsulfonyl group, provided that when R² isa chlorine atom, a bromine atom or an iodine atom, R¹ is a halogen atomor a halogen-substituted C₁ -C₂ alkyl group-and R³ is a C₁ -C₆alkylcarbonyl group, a C₁ -C₆ alkyloxycarbonyl group, a C₁ -C₆alkyloxycarbonyl group substituted with C₁ -C₂ alkyloxy or phenyl, abenzoyl group, a phenoxycarbonyl group or a halogen-substituted C₁ -C₆alkylcarbonyl group exhibit strong herbicidal potency, and some of themshow noticeable selectivity between crop plants and weeds. Thisinvention is based on the above finding.

In the foregoing and subsequent descriptions, the carbon numberindicates that of a group (i.e. alkyl, alkenyl or alkynyl) immediatelyfollowing the same. In case of a C₁ -C₆ alkylcarbonyl group, forinstance, the carbon number indicates that of its alkyl portion and doesnot include that of its carbonyl portion. In case of a C₃ -C₄alkynyloxycarbonyl group, the carbon number indicates that of itsalkynyl portion and does not include that of its carbonyl portion.

Also, a group substituted with a substituent(s) (e.g. C₁ -C₂ alkyloxy,phenyl, methyl) covers a group bearing 1 or 2 substituents. Forinstance, a C₁ -C₆ alkyloxycarbonyl group substituted with C₁ -C₂alkyloxy or phenyl covers a C₁ -C₆ alkyloxycarbonyl group substitutedwith one or two C₁ -C₂ alkyloxys and a C₁ -C₆ alkyloxycarbonyl groupsubstituted with 1 or 2 phenyls. The term "halogen-substituted" isintended to mean usually "substituted with not more than five halogens",particularly "substituted with not more than three halogens".

The iminothiazoline compounds (I) produce generally strong herbicidalactivity against a wide variety of weeds including broad-leaved weedsand Graminaceous weeds in agricultural plowed fields by foliar or soiltreatment without producing any material phytotoxicity to crop plants.Examples of the broad-leaved weeds include common purslane (Portulacaoleracea), common chickweed (Stellaria media), common lambsquarters(Chenopodium album), redroot pigweed (Amaranthus retroflexus), radish(Raphanus sativus), wild mustard (Sinapis arvensis), shepherdspurse(Capsella bursa-pastoris), hemp sesbania (Sesbania exaltata), sicklepod(Cassia obtusifolia), velvetleaf (Abutilon theophrasti), prickly sida(Sida spinosa), field pansy (Viola arvensis), catchweed bedstraw (Galiumaparine), ivyleaf morningglory (Ipomoea hederacea), tall morningglory(Ipomoea purpurea), field bindweed (Convolvulus arvensis), purpledeadnettle (Lamium purpureum), henbit (Lamium amplexicaure), jimsonweed(Datura stramonium), black nightshade (Solanum nigrum), persianspeedwell (Veronica persica), common cocklebur (Xanthium pensylvanicum),common sunflower (Helianthus annuus), scentless chamomile (Matricariaperforata), corn marigold (Chrysanthemum segetum), etc. Examples ofGraminaceous weeds include japanese millet (Echinochloa frumentacea),barnyardgrass (Echinochloa crus-galli), green foxtail (Setaria viridis),yellow foxtail (Setaria glauca), southern crabgrass (Digitariaciliaris), large crabgrass (Digitaria sanguihalls) annual bluegrass (Poaannua), blackgrass (Alopecurus myosuroides), oats (Avena sativa), wildoats (Avena fatua), johnsongrass (Sorghum halepense), quackgrass(Agropyron repens), downy brome (Bromus tectorum), giant foxtail(Setaria faberi), fall panicum (Panicurn dichotomiflorum), shattercane(Sorghum bicolor), bermudagrass (Cynodon dactylon), etc. Advantageously,the iminothiazoline compounds (I) do not show any material chemicalinjury to various agricultural crops such as corn, wheat, barley, riceplant, soybean, cotton, sugar beet, etc., particularly to cotton.

The iminothiazoline compounds (I) are also effective in exterminatingpaddy field Weeds including Graminaceous weeds such as barnyardgrass(Echinochloa oryzicola), broad-leaved weeds such as commonfalsepimpernel (Lindernia procumbens), indian toothcup (Rotala indica),waterwort (Elatine triandra) and Ammannia multiflora, Cyperaceous weedssuch as umbrella sedge (Cyperus difformis), hardstem bulrush (Scirpusjuncoides), needle spikerush (Eleocharis acicularis) and water nutgrass(Cyperus serotinus), and others such as monochoria (Monochoriavaginalis) and arrowhead (Sagittaria pygmaea) without producing anyphytotoxicity to rice plants on flooding treatment.

Among the iminothiazoline compounds (I), preferred are those wherein R¹is a trifluoromethyl group; those wherein R² is a methyl group or anethyl group; and those wherein R³ is a C₁ -C₆ alkylcarbonyl group, a C₁-C₆ alkyloxycarbonyl group, a C₁ -C₆ alkyloxycarbonyl group substitutedwith C₁ -C₂ alkyloxy or phenyl, a cyclo(C₃ -C₆)alkylcarbonyl group, acyclo(C₃ -C₆)alkylcarbonyl group substituted with methyl, a cyclo(C₃-C₆)alkyloxycarbonyl group, a benzoyl group or a halogen-substituted C₁-C₆ alkylcarbonyl group. With respect to R₃, more preferred are a C₁ -C₄alkylcarbonyl group, a C₁ -C₄ alkyloxycarbonyl group, a C₁ -C₄alkyloxycarbonyl group substituted with C₁ -C₂ alkyloxy or phenyl, acyclo(C₃ -C₆)alkylcarbonyl group, a cyclo(C₃ -C₆)alkylcarbonyl groupsubstituted with methyl, a cyclo(C₃ -C₆)alkyloxycarbonyl group, abenzoyl group and a halogen-substituted C₁ -C₄ alkylcarbonyl group;furthermore preferred are a C₁ -C₄ alkylcarbonyl group, a C₁ -C₄alkyloxycarbonyl group and a halogen-substituted C₁ -C₄ alkylcarbonylgroup; still more preferred is a halogen-subtituted C₁ -C₄ alkylcarbonylgorup; the most preferred are a difluoroacetyl group or atrifuluoroacetyl group. Typical examples of the most preferred compoundsare as follows: ##STR3##

The iminothiazoline compounds (I) can be produced by various procedures,of which typical examples are shown in the following schemes I to III.##STR4## wherein R¹, R², R³ are each as defined above R⁴ is a hydrogenatom or a methyl group, R⁵ is a C₁ -C₆ alkyl group, a C₁ -C₆ alkyloxygroup, a C₁ -C₆ alkyloxy group substituted with C₁ -C₂ alkyloxy orphenyl, a cyclo(C₃ -C₆)alkyl group, a cyclo(C₃ -C₆)alkyl groupsubstituted with methyl, a cyclo(C₃ -C₆)alkyloxy group, a phenyl group,a phenoxy group, a halogen-substituted C₁ -C₆ alkyl group or a benzylgroup, R⁶ is a C₁ -C₃ alkyl group, R⁷ is a halogen atom or ahalogen-substituted C₁ -C₂ alkyl group, R⁸ is a C₁ -C₆ alkyl group, a C₁-C₆ alkyloxy group, a C₁ -C₆ alkyloxy group substituted with C₁ -C₂alkyloxy or phenyl, a phenyl group, a phenyloxy group or ahalogen-substituted C₁ -C₆ alkyl group. R⁹ is a formyl group, a C₁ -C₆alkylcarbonyl group, a C₃ -C₄ alkenyloxycarbonyl group, a C₃ -C₄alkynyloxycarbonyl group, a C₁ -C₆ alkyloxycarbonyl group, a C₁ -C₆alkyloxycarbonyl group substituted with C₁ -C₂ alkyloxy or phenyl, acyclo(C₃ -C₆)alkylcarbonyl group, a cyclo(C₃ -C₆)alkylcarbonyl groupsubstituted with methyl, a cyclo (C₃ -C₆ ) alkyloxycarbonyl group, abenzoyl group, a phenoxycarbonyl group, a halogen-substituted C₁ -C₆alkylcarbonyl group or a halogen-substituted C₁ -C₃ alkylsulfonyl group,R¹⁰ is a C₁ -C₆ alkyl group, a C₁ -C₆ alkyl group substituted with C₁-C₂ alkyloxy or phenyl, a C₃ -C₄ alkenyl group or a C₃ -C₄ alkynylgroup, R¹¹ is a chlorine atom, a bromine atom or an iodine atom and Xand Y are each-a halogen atom.

Procedures for production of the iminothiazoline compounds (I) asillustratively shown in the above schemes I to III will be hereinafterexplained in detail.

Procedure (a):

The iminothiazoline compound (I) wherein R² is a methyl group or anethyl group and R³ is --CO--R⁵ is obtainable by reacting theiminothiazolidine compound (II) with a base.

The reaction is usually carried out in a solvent at a temperature of 0°to 200° C. for a period of 1 to 30 hours. In the reaction, the base isused in an amount of 1 to 50 equivalents to one equivalent of theiminothiazolidine compound (II). As the solvent, there may beexemplified aliphatic hydrocarbons (e.g. hexane, heptane), aromatichydrocarbons (benzene, toluene, xylene), ethers (e.g. diisopropyl ether,dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), alcohols(e.g. methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol,methylcellosolve, diethylene glycol, glycerin), acid amides (e.g.N,N-dimethylformamide), sulfur compounds (e.g. dimethylsulfoxide,sulforan), water, etc. and their mixtures. Examples of the base are aninorganic base (e.g. sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate), an alkali metal alkoxide (e.g. sodiummethoxide, sodium ethoxide, potassium t-butoxide, sodium t-butoxide),etc.

After completion of the reaction, the reaction mixture may be subjectedto after-treatment in a per se conventional manner such as extractionwith an organic solvent and concentration. If necessary, anypurification method (e.g. chromatography, recrystallization, etc.) maybe further adopted to give the objective compound (I), i.e. Compound(I-1).

Procedure (b):

The iminothiazoline compound (i) wherein R² is a methyl group or anethyl group and R³ is --CO--R⁵ can be also produced by the reaction ofthe iminothiazolidine compound (III) with a base.

This reaction is usually carried out in a solvent at a temperature of 0°to 200° C. for a period of 1 to 30 hours. The base may be used in anamount of 0.5 to 50 equivalents to one equivalent of theiminothiazolidine compound (III).

The solvent and the base may be chosen from those as exemplified inProceudre (a). Also, the reaction mixture may be subjected toafter-treatment in the same way as in Procedure (a) to give theobjective compound (I), i.e. Compound (I-1).

Procedure (c):

The iminothiazoline compound (I) wherein R² is a methyl group or anethyl group and R³ is the same as represented by R⁹ is obtainable by thereaction of the iminothiazoline compound (IV) with an acid chloride (V),an acid anhydride (XIV) or an acid (XXXI) in the presence of a base.

The reaction is usually performed in a solvent at a temperature of 0° to200° C. for a period of 1 to 30 hours. The acid chloride (V), the acidanhydride (XIV) or the acid (XXXI) may be used in an amount of 1 to 10equivalents to one equivalent of the iminothiazoline compound (IV), andthe base may be used in an amount of 1 to 50 equivalents to oneequivalent of the iminothiazoline compound (IV). When the reaction iscarried with the acid (XXXI) as the reagent, a condensing agent such asdicyclohexylcarbodiimide or1-ethyl-3-(3-dimethylaminopropyl)carbodiimide is normally used in anamount of 1 to 10 equivalents to one equivalent of the iminothiazolinecompound (IV). As the solvent, there may be exemplified aliphatichydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatichydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons(e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene,dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether,dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones(e.g. acetone, methylethylketone, methylisobutylketone, isophorone,cyclohexanone), esters (e.g. ethyl formate, ethyl acetate, butylacetate, diethyl carbonate), nitro compounds (e.g. nitroethane,nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiaryamines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine,N-methylmorpholine), acid amides (e.g. N,N-dimethylformamide), sulfurcompounds (e.g. dimethylsulfoxide, sulforan), etc. and their mixtures.As the base, there may be employed an organic base (e.g. pyridine,triethylamine, N,N-diethylaniline) or the like.

After completion of the reaction, the reaction mixture may be subjectedto after-treatment in the same manner as in Procedure (a) to give theobjective compound (I), i.e. Compound (I-2).

Procedure (d):

The iminothiazoline compound (I) wherein R² is a methyl group or anethyl group and R³ is --CO--OR¹⁰ can be produced by reacting theiminothiazoline compound (I-6) with the alcohol (XV) in the presence ofa base.

The reaction is usually carried out in a solvent at a temperature of 0°to 200° C. for a period of 1 to 30 hours. The alcohol (XV) and the basemay be used respectively in amounts of 1 to 10 equivalents and 0.5 to 50equivalents to one equivalent of the iminothiazoline compound (I-6). Asthe solvent, there are employed aliphatic hydrocarbons (e.g. hexane,heptane, ligroin), aromatic hydrocarbons (e.g. benzene, toluene,xylene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane,tetrahydrofuran, diethyleneglycol dimethyl ether), alcohols (e.g.methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol,methylcellosolve, diethyleneglycol, glycerin), acid amides (e.g.N,N-dimethylformamide), sulfur compounds (e.g. dimethylsulfoxide,sulforan), water, etc. and their mixtures. Examples of the base may bean inorganic base (e.g. sodium hydroxide, potassium hydroxide), analkali metal alkoxide (e.g. sodium methoxide, sodium ethoxide), etc.

After completion of the reaction, the reaction mixture may be subjectedto after-treatment in the same manner as in Procedure (a) to give theobjective compound (I), i.e. Compound (I-3).

Procedure (e):

The iminothiazoline compound (I) wherein R² is a methyl group or anethyl group and R³ is --CONH--R⁶ is prepared by reacting theiminothiazolidine compound (VI) with a base.

This reaction is usually carried out in a solvent at a temperature of 0°to 200° C. for a period of 1 to 30 hours. The base is used in an amountof 0.5 to 50 equivalents to one equivalent of the iminothiazolidinecompound (VI). Examples of the solvent are those as used in Procedure(a). As the base, there may be employed an alkali metal alkoxide (e.g.sodium methoxide, sodium ethoxide) or the like.

After completion of the reaction, the reaction mixture is subjected toafter-treatment in the same way as in Procedure (a) to give theobjective compound (I), i.e. Compound (I-4).

Procedure (f):

The iminothiazoline compound (I) wherein R¹ is the same as representedby R⁷, R², is a chlorine atom, a bromine atom or an iodine atom and R³is --CO--R⁸ is prepared by reacting the iminothiazoline compound (VII)with a halogenating agent.

The reaction is usually carried out in a solvent at a temperature of 50°to 150° C. for a period of 2 to 10 hours. The halogenating agent may beused in an amount of 1 to 10 equivalents to one equivalent of thecompound (VII). Examples of the solvent are aliphatic hydrocarbons (e.g.hexane, heptane), halogenated hydrocarbons (e.g. chloroform, carbontetrachloride, dichloroethane), ethers (e.g. diisopropyl ether, dioxane,tetrahydrofuran, diethyleneglycol dimethyl ether), etc. and theirmixtures. As the halogenating agent, there may be exemplifiedN-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, etc.

After completion of the reaction, the reaction mixture is after-treatedin the same way as in Procedure (a) to give the objective compound (I),i.e. Compound (I-5) or (I-8).

Procedure (g):

The iminothiazoline compound (I) wherein R¹ is the same as representedby R⁷, R² is a chlorine atom, a bromine atom or an iodine atom and R³ is--CO--R⁸ is obtainable by reacting the iminothiazoline compound (VIII)with a halogenating agent.

The reaction is usually carried out in a solvent at a temperature of 50°to 150° C. for a period of 2 to 10 hours. The halogenating agent may beused in an amount of 1 to 10 equivalents to one equivalent of theiminothiazoline compound (VIII). Examples of the solvent and thehalogenating agent may be those as exemplified in Procedure (f).

After completion of the reaction, the reaction mixture is after-treatedin the same way as in Procedure (a) to give the objective compound (I),i.e. Compound (I-5).

Typical examples of the iminothiazoline compounds (I) produced by theabove procedures are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR5##                      (I)                                            R.sup.1      R.sup.2 R.sup.3                                                  ______________________________________                                        CF.sub.3     CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3     C.sub.2 H.sub.5                                                                       CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH.sub.3                                        CF.sub.3     CH.sub.3                                                                              CO.sub.2 (i)C.sub.3 H.sub.7                              CF.sub.3     C.sub.2 H.sub.5                                                                       CO.sub.2 (i)C.sub.3 H.sub.7                              CF.sub.3     CH.sub.3                                                                              CO.sub.2 (n)C.sub.3 H.sub.7                              CF.sub.3     CH.sub.3                                                                               ##STR6##                                                CF.sub.3     CH.sub.3                                                                               ##STR7##                                                CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                     CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH.sub.2 CHCH.sub.2                             CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                     CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH.sub.2 CCH                                    CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                     CF.sub.3     C.sub.2 H.sub.5                                                                       CO.sub.2 CH.sub.2 CCH                                    CF.sub.3     C.sub.2 H.sub.5                                                                       CO.sub.2 CH.sub.3                                        CF.sub.3     C.sub.2 H.sub.5                                                                       COCH.sub.2 CH(CH.sub.3).sub.2                            CF.sub.3     CH.sub.3                                                                               ##STR8##                                                CF.sub.3     CH.sub.3                                                                              COCH.sub.2 C(CH.sub.3).sub.3                             CF.sub.3 O   CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3 O   CH.sub.3                                                                              CO.sub.2 (i)C.sub.3 H.sub.7                              CF.sub.3     C.sub.2 H.sub.5                                                                        ##STR9##                                                CF.sub.3     C.sub.2 H.sub.5                                                                       CO.sub.2 (n)C.sub.3 H.sub.7                              CF.sub.3     CH.sub.3                                                                              CO(i)C.sub.3 H.sub.7                                     CF.sub.3     CH.sub.3                                                                              CO(n)C.sub.4 H.sub.9                                     CF.sub.3 O   C.sub.2 H.sub.5                                                                       CO.sub.2 (i)C.sub.3 H.sub.7                              CF.sub.3     CH.sub.3                                                                               ##STR10##                                               CF.sub.3     CH.sub.3                                                                              COC(CH.sub.3).sub.3                                      CF.sub.3     CH.sub.3                                                                              COCH.sub.2 CH(CH.sub.3).sub.2                            CF.sub.3     CH.sub.3                                                                              COCH(CH.sub.3)CH.sub.2 CH.sub.3                          CF.sub.3     CH.sub.3                                                                              COC.sub.6 H.sub.5                                        F            CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                 Br           CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                 Cl           CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                 I            CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3 CF.sub.2                                                                          C.sub.2 H.sub.5                                                                       CO.sub.2 (i)C.sub.3 H.sub.7                              CF.sub.2 HCF.sub.2 O                                                                       C.sub.2 H.sub.5                                                                       CO.sub.2 (i)C.sub.3 H.sub.7                              CF.sub.3     C.sub.2 H.sub.5                                                                       CO.sub.2 CH.sub.2 CH.sub.2 CCH                           CF.sub.3     C.sub.2 H.sub.5                                                                       CO(n)C.sub.5 H.sub.11                                    CF.sub.3     C.sub.2 H.sub.5                                                                       CO.sub.2 (n)C.sub.5 H.sub.11                             CF.sub.3     C.sub.2 H.sub.5                                                                       COC.sub.2 H.sub.5                                        CF.sub.3     C.sub.2 H.sub.5                                                                       COCH.sub.3                                               CF.sub.3     Br      CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3     Cl      CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3     Br      COC.sub.6 H.sub.5                                        CF.sub.3     Br      CO.sub.2 (i)C.sub.3 H.sub.7                              CF.sub.3     Br      CO.sub.2 CH.sub.3                                        CF.sub.3     Br      CO(n)C.sub.3 H.sub.7                                     CF.sub.3     Br      CO.sub.2 (n)C.sub.4 H.sub.9                              F            Br      CO.sub.2 C.sub.2 H.sub.5                                 Br           Br      CO.sub.2 C.sub.2 H.sub.5                                 Cl           Br      CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3     Br      CO.sub.2 C.sub.6 H.sub.5                                 CF.sub.3     Br      CO.sub.2 (n)C.sub.3 H.sub.7                              CF.sub.3     I       CO.sub.2 C.sub.2 H.sub.5                                 CF.sub.3     Br      CO.sub.2 CH.sub.2 C.sub.6 H.sub.5                        CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH.sub.2 CCCH.sub.3                             CF.sub.3     C.sub.2 H.sub.5                                                                       CONHC.sub.3 H.sub.7                                      CF.sub.3     CH.sub.3                                                                              COC.sub.2 H.sub.5                                        CF.sub.3     CH.sub.3                                                                              CO(n)C.sub.3 H.sub.7                                     CF.sub.3     CH.sub.3                                                                              COCH.sub.2 C.sub.6 H.sub.5                               CF.sub.3     C.sub.2 H.sub.5                                                                       CO(n)C.sub.3 H.sub.7                                     CF.sub.3     C.sub.2 H.sub.5                                                                       CO(i)C.sub.3 H.sub.7                                     CF.sub.3     C.sub.2 H.sub.5                                                                       COCH.sub.2 C(CH.sub.3).sub.3                             F            CH.sub.3                                                                              CO(CH.sub.2).sub.3 Cl                                    Cl           CH.sub.3                                                                              COCH.sub.2 CH.sub.2 Br                                   CF.sub.3     CH.sub.3                                                                              CONHC.sub.2 H.sub.5                                      CF.sub.3     C.sub.2 H.sub.5                                                                       SO.sub.2 CF.sub.3                                        CF.sub.3     CH.sub.3                                                                              COCH.sub.2 CH.sub.2 Cl                                   CF.sub.3     Br      COCH.sub.3                                               CF.sub.3     CH.sub.3                                                                              CO(n)C.sub.5 H.sub. 11                                   CF.sub.3     CH.sub.3                                                                               ##STR11##                                               CF.sub.3     CH.sub.3                                                                              CO.sub.2 CH.sub.2 CHCHCH.sub.3                           CF.sub.3     CH.sub.3                                                                              COCH.sub.2 Cl                                            CF.sub.3     CH.sub.3                                                                              CO(CH.sub.2).sub.3 Cl                                    CF.sub.3     CH.sub.3                                                                               ##STR12##                                               CF.sub.3     C.sub.2 H.sub.5                                                                       CONHCH.sub.3                                             CF.sub.3     CH.sub.3                                                                              COCH.sub.2 Br                                            CF.sub.3     CH.sub.3                                                                              COCF.sub.3                                               CF.sub.3     C.sub.2 H.sub.5                                                                       COCF.sub.3                                               CF.sub.3     Br      COCF.sub.3                                               CF.sub.3     CH.sub.3                                                                              COC.sub.2 F.sub.5                                        CF.sub.3     C.sub.2 H.sub.5                                                                       COC.sub.2 F.sub.5                                        CF.sub.3     CH.sub.3                                                                              COC.sub.3 F.sub.7                                        CF.sub.3 O   CH.sub.3                                                                              COCH.sub.3                                               CF.sub.3 O   CH.sub.3                                                                              COCF.sub.3                                               CF.sub.3     C.sub.2 H.sub.5                                                                        ##STR13##                                               CF.sub.3     CH.sub.3                                                                              COCHF.sub.2                                              CF.sub.3     CH.sub.3                                                                              COCH.sub.2 F                                             CF.sub.3     C.sub.2 H.sub.5                                                                       COCHF.sub.2                                              CF.sub.3 O   C.sub.2 H.sub.5                                                                       COCH.sub.3                                               CF.sub.3 O   C.sub.2 H.sub.5                                                                       COCF.sub.3                                               CF.sub.3 O   CH.sub.3                                                                              COCHF.sub.2                                              CF.sub.3 O   C.sub.2 H.sub.5                                                                       COCHF.sub.2                                              ______________________________________                                    

The compounds (III), (XI), (IV) and (VIII) used as the startingmaterials for production of the iminothiazoline compound (I) in theabove procedures are novel and may be produced, for instance, by theprocesses as set forth below.

Compound (III):

The compound (III) is produced by reacting the aniline compound (IX)with an isothiocyanate (X).

The reaction is usually carried out in a solvent at a temperature of 0°to 200° C. for a period of 1 to 30 hours. The isothiocyanate (X) isnormally used in an amount of 1 to 5 equivalents to one equivalent ofthe aniline compound (IX). As the solvent, there may be employedaliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether),aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenatedhydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane,chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropylether, dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether),ketones (e.g. acetone, methylethylketone, methylisobutylketone,isophoron, cylcohexanone), nitro compounds (e.g. nitroethane,nitrobenzene), acid amides (e.g. N,N-dimethylformamide), sulfurcompounds (e.g. dimethylsulfoxide, sulforan), etc. and their mixtures.For acceleration of the reaction, an acid (e.g. sulfuric acid) or a base(e.g. sodium methoxide) may be present in the reaction system.

After completion of the reaction, the reaction mixture is after-treatedby a per se conventional procedure. For instance, the mixture isextracted with an organic solvent, followed by concentration. Ifnecessary, the reaction product may be purified by chromatography orrecrystallization to give the objective compound (III).

Still, the above reaction can proceed through the compound (III) to theiminothiazoline compound (I) in a single operation depending upon thethe kind of the compound (III) and the reaction conditions (cf.Procedure (b)).

In an alternative way, the compound (III) may be produced by reactingthe iminothiazolidine compound (II) with a base. This reaction isordinarily carried out in a solvent at a temperature of 0° to 200° C.for a period of 1 to 30 hours. The base is used normally in an amount of1 to 50 equivalents to one equivalent of the iminothiazolidine compound(II). As the solvent, there may be employed aliphatic hydrocarbons (e.g.hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g.benzene, toluene, xylene), ethers (e.g. diethyl ether, diisopropylether, dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether),alcohols (e.g. methanol, ethanol, isopropanol, t-butanol, octanol,cyclohexanol, methylcellosolve, diethylene glycol, glycerin), acidamides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfurcompounds (e.g. dimethylsulfoxide, sulforan), etc. and their mixtures.Examples of the base are an inorganic base (e.g. sodium hydroxide,potassium hydroxide), an alkali metal alkoxide (e.g. sodium methoxide,sodium ethoxide, sodium t-butoxide), etc.

After completion of the reaction, the reaction mixture is after-treatedin the same manner as in the previous reaction.

In another alternative way, the compound (III) is obtainable by reactingthe iminothiazolidine compound (XI) with an acid chloride (XII) in thepresence of a base.

This reaction is usually performed in a solvent at a temperature of 0°to 200° C. for a period of 1 to 30 hours. The acid chloride (XII) andthe base are respectively used in amounts of 1 to 10 equivalents and 1to 50 equivalents to one equivalent of the iminothiazolidine compound(XI). Examples of the solvent are aliphatic hydrocarbons (e.g. hexane,heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene,toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbontetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers(e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran,diethyleneglycol dimethyl ether), ketones (e.g. acetone,methylethylketone, methylisobutylketone, isophoron, cyclohexanone),esters (e.g. ethyl formate, ethyl acetate, butyl acetate, diethylcarbonate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles(e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine,triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine),acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfurcompounds (e.g. dimethylsulfoxide, sulforan), etc. and their mixtures.As the base, there may be used an organic base (e.g. pyridine,triethylamine, N,N-diethylaniline) or the like.

After completion of the reaction, the reaction mixture is after-treatedin the same manner as in the previous reaction.

Typical examples of the compound (III) as obtainable by the aboveprocedures are as follows:

                  TABLE 2                                                         ______________________________________                                         ##STR14##                    (III)                                           R.sup.1      R.sup.4 Rhu 6                                                    ______________________________________                                        CF.sub.3     H       OC.sub.2 H.sub.5                                         CF.sub.3     CH.sub.3                                                                              OC.sub.2 H.sub.5                                         CF.sub.3     H       OCH.sub.3                                                CF.sub.3     H       O(i)C.sub.3 H.sub.7                                      CF.sub.3     CH.sub.3                                                                              O(i)C.sub.3 H.sub.7                                      CF.sub.3     H       O(n)C.sub.3 H.sub.7                                      CF.sub.3     H                                                                                      ##STR15##                                               CF.sub.3     H                                                                                      ##STR16##                                               CF.sub.3 O   CH.sub.3                                                                               ##STR17##                                               Cl           H       CH.sub.3                                                 Br           CH.sub.3                                                                              C.sub.2 H.sub.5                                          CF.sub.3     CH.sub.3                                                                              CF.sub.3                                                 CF.sub.3 O   H       CF.sub.3                                                 CF.sub.3     H       CF.sub.3                                                 CF.sub.3     H       CH.sub.2 C(CH.sub.3).sub.3                               CF.sub.3     H                                                                                      ##STR18##                                               CF.sub.3     H       CH.sub.2 CH.sub.2 Cl                                     CF.sub.3     CH.sub.3                                                                              Chd 2 H.sub. 5                                           CF.sub.3     H       (i)C.sub.3 H.sub.7                                       CF.sub.3     CH.sub.3                                                                              (n)C.sub.4 H.sub.9                                       CF.sub.3     H       OC.sub.6 H.sub.5                                         CF.sub.3     CH.sub.3                                                                              (CH.sub.2).sub.4 Cl                                      CF.sub.3 CF.sub.2                                                                          H       C hd 2 H.sub.5                                           F            H       C.sub.2 H.sub.5                                          CF.sub.2 HCF.sub.2 O                                                                       CH.sub.3                                                                              C.sub.6 H.sub.5                                          CF.sub.3     CH.sub.3                                                                              CHF.sub.2                                                CF.sub.3     H       CHF.sub.2                                                ______________________________________                                    

Compound (XI):

The compound (XI) can be produced by reacting the aniline compound(XIII) with hydrogen sulfide.

This reaction may be accomplished in a solvent in the presence of a baseat a temperature of 0° to 30° C. for a period of 5 minutes to 5 hours.Hydrogen sulfide is used in an equimolar amount or more to the anilinecompound (XIII), while the base may be employed in a catalytic amount.As the solvent, there may be exemplified aliphatic hydrocarbons (e.g.hexane, heptane, ligroin, petroleum ether), ethers (e.g. diethyl ether,diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethylether), alcohols (e.g. methanol, ethanol, isopropanol, t-butanol,octanol, cyclohexanol, methylcellosolve, diethylene glycol, glycerin),nitro compounds (e.g. nitroethane, nitrobenzene), tertiary amines (e.g.pyridine, triethylamine, N,N-diethylaniline, tributylamine,N-methylmorpholine), acid amies (e.g. formamide, N,N-dimethylformamide,acetamide), sulfur compounds (e.g. dimethylsulfoxide, sulforan), etc.and their mixtures. The base is chosen from an organic base (e.g.pyridine, triethylamine and N,N-diethylaniline) or the like.

After completion of the reaction, the reaction mixture is post-treatedin the same manner as in the previous reaction.

Typical examples of the compounds (XI) as obtainable by the aboveprocedure are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                         ##STR19##                    (XI)                                                   R.sup.1  R.sup.4                                                       ______________________________________                                               CF.sub.3 H                                                                    CF.sub.3 CH.sub.3                                                             CF.sub.3 O                                                                             H                                                                    F        H                                                                    Cl       H                                                                    Br       CH.sub.3                                                             CF.sub.3 CF.sub.2                                                                      CH.sub.3                                                             CF.sub.2 HCF.sub.2 O                                                                   CH.sub.3                                                      ______________________________________                                    

Compound (IV):

The compound (IV) is produced by reacting the iminothiazoline compound(I-7) with trifluoroacetic acid.

This reaction is usually carried out in the presence or absence of asolvent at a temperature of 0° to 0° C. for a period of 1 to 10 hours.The amount of trifluoroacetic acid to be used as the reagent is usuallyfrom about 1 to 100 equivalents to one equivalent of the iminothiazolinecompound (I-7). As the solvent, there may be employed aliphatichydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatichydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons(e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene,dichlorobenzene), ketones (e.g. acetone, methylethylketone,methylisobutylketone, isophoron, cylcohexanone), nitro compounds (e.g.nitroethane, nitrobenzene), nitriles (e.g. acetonitrile,isobutyronitrile), acid amides (e.g. formamide, N,N-dimethylformamide,acetamide), sulfur compounds (e.g. dimethylsulfoxide, sulforan), water,etc. and their mixtures.

After completion of the reaction, the reaction mixture is post-treatedin the same manner as in the previous reaction.

Besides, the compound (IV) is obtainable by reacting the compound (I-9)with aqueous hydrochloric acid.

This reaction is usually performed in a solvent at a temperature of 0°to 200° C. for a period of 0.5 to 30 hours. Hydrochloric acid is used inan amount of 1 to 1000 equivalents to one equivalent of the compound(I-9). Examples of the solvent are alcohols (e.g. methanol, ethanol,isopropanol, methyl cellosolve), ethers (e.g. diethyl ether, diisopropylether, dioxane, tetrahydrofuran), water, etc., and their mixtures.

After completion of the reaction, the reaction mixture is post-treatedin the same manner as in the previous reaction.

Typical examples of the compounds (IV) as obtained by the aboveprocedure are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                         ##STR20##                    (IV)                                                   R.sup.1  R.sup.4                                                       ______________________________________                                               CF.sub.3 H                                                                    CF.sub.3 CH.sub.3                                                             CF.sub.3 O                                                                             CH.sub.3                                                             F        H                                                                    Cl       H                                                                    Br       CH.sub.3                                                             CF.sub.3 CF.sub.2                                                                      CH.sub.3                                                             CF.sub.2 HCF.sub.2 O                                                                   CH.sub.3                                                      ______________________________________                                    

Compound (VIII):

The compound (VIII) is obtainable by reacting the iminothiazolinecompound (I-8) with a reducing agent such as tributyltin hydride.

The reaction is usually performed in a solvent at a temperature of 0° to200° C. for a period of 1 to 30 hours. The amount of the reducing agentmay be from about 1 to 10 equivalents to one equivalent of the compound(I-8).

There may be used as the solvent aliphatic hydrocarbons (e.g. hexane,heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene,toluene, xylene), ethers (e.g. diethyl ether, diisopropyt ether,dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether), ketones(e.g. acetone, methylethylketone, methylisobutylketone, isophoron,cyclohexanone), esters (e.g. ethyl formate, ethyl acetate, butylacetate, diethyl carbonate), nitro compounds (e.g. nitroethane,nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), acidamides (e.g. N,N-dimethylformamide), sulfur compounds (e.g.dimethylsulfoxide, sulforan), etc. and their mixtures.

After completion of the reaction, the reaction mixture is post-treatedin the same manner as in the previous reaction.

Typical examples of the compound (VIII) as obtainable by the aboveprocedure are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                         ##STR21##                   (VIII)                                           R.sup.7      R.sup.8                                                          ______________________________________                                        CF.sub.3     OC.sub.2 H.sub.5                                                 CF.sub.3     C.sub.2 H.sub.5                                                  CF.sub.3     CH.sub.3                                                         CF.sub.3 CF.sub.2                                                                          CH.sub.3                                                         F            OCH.sub.3                                                        Cl           OCH.sub.2 CH.sub.2 CH.sub.3                                      Br           (CH.sub.2).sub.3 CH.sub.3                                        CF.sub.3 CF.sub.2                                                                           ##STR22##                                                       CF.sub.3                                                                                    ##STR23##                                                       CF.sub.3     CF.sub.3                                                         CF.sub.3 O   CF.sub.3                                                         ______________________________________                                    

The iminothiazolidine compound (II) may be produced by the method asdescribed in J.Am. Chem. Soc., p.1079 (1984). Namely, the compound (II)is obtainable by reacting the aniline compound (XVI) with anisothiocyanate (X) to give the thiourea (XVII) and treating the latterwith a halogenating agent. Alternatively, the compound (II) can beproduced by reacting the thiourea (XVII: R=OEt) with sodium methoxide togive the thiourea (XIX) and reacting the latter with a halogenatingagent to give the iminothiazolidine compound (XX), followed by treatmentwith the acid chloride (XII) in the presence of a base.

The compound (IX) is obtainable by reacting the aniline compound (XXI)with an alkynyl bromide (XXII) or an alkynyl methanesulfonate (XXXI) inthe presence of a base. The compound (XIII) is produced by reacting theaniline compound (XXIII) with an alkynyl bromide (XXII) in the presenceof a base. The compound (I-7) is produced by reacting the compound (I-6)with potassium t-butoxide. The compound (VI) is prepared by reacting theiminothiazolidine compound ##STR24## with the amine (XXV).

The iminothiazolidine compound (VII) may be obtained by reacting thethiourea (XXVI) with a halide (XXVII) to give the iminothiazoline(XXVIII), followed by treatment with an acid chloride (XXIX). Theiminothiazolidine compound (VII) is also produced by treating thethiourea (XXX) with a halide (XXVII).

The iminothiazoline compound (I-8) can be obtained by reacting theiminothiazolidine (VII) with a halogenating agent (cf. Procedure (f)).

For the practical usage of the iminothiazoline (I), it is usuallyformulated with a conventional solid or liquid carrier(s)-or diluent(s)as well as a surface active agent(s) or auxiliary agent(s) into aconventional preparation form such as emulsifiable concentrate, wettablepowder, suspension, granules or water dispersible granules. The contentof the iminothiazoline compound (I) as the active ingredient in suchpreparation form is normally within a range of about 0.02 to 90% byweight, preferably of about 0.05 to 80% by weight. Examples of the solidcarrier or diluent are fine powders or granules of kaolin clay,attapulgite clay, bentonite, terra alba, pyrophyllite, talc,diatomaceous earth, calcite, walnut shell powders, urea, ammoniumsulfate and synthetic hydrous silica, etc. As the liquid carrier ordiluent, there may be exemplified aromatic hydrocarbons (e.g. xylene,methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol,cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone),vegetable oil (e.g. soybean oil, cotton seed oil), dimethylsulfoxide,N,N-dimethylformamide, acetonitrile, water, etc.

The surface active agent used for emulsification, dispersing orspreading may be of any type, for instance, either anionic or non-ionic.Examples of the surface active agent include alkylsulfates,alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, phosphatesof polyoxyethylenealkylaryl ethers, polyoxyethylene alkyl ethers,polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene blockcopolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fattyacid esters, etc. Examples of the auxiliary agent includeligninsulfonates, sodium alginate, polyvinyl alcohol, gum arabic, CMC(carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.

The iminothiazoline compound (I) thus formulated in any suitablepreparation form is useful for pre-emergence or post-emergence controlof undesired weeds by soil or foliar treatment as well as floodfallowing treatment. These treatments include application to the soilsurface prior to or after planting, incorporation into the soil prior toplanting or transplanting, etc. The foliar treatment may be effected byspraying the herbicidal composition containing the iminothiazolinecompound (I) over the top of plants. It may also be applied directly tothe weeds if care is taken to keep the chemical off the crop foliage.

The dosage of the iminothiazoline compound (I) may vary depending on theprevailing weather conditions, the formulation used, the prevailingseason, the mode of application, the soil involved, the crop and weedspecies, etc. Generally, however, the dosage is from about 10 to 5000grams, preferably from about 20 to 2000 grams, of the active ingredientper hectare. The herbicidal composition of the invention formulated inthe form of an emulsifiable concentrate, a wettable powder or asuspension may ordinarily be employed by diluting it with water at avolume of about 100 to 1000 liters per hectare, if necessary, withaddition of an auxiliary agent such as a spreading agent. Thecomposition formulated in the form of granules may be normally appliedas such without dilution.

Examples of the spreading agent include, in addition to the surfaceactive agents as noted above, polyoxyethylene resin acid (ester),ligninsulfonate, abietylenic acid salt, dinaphthylmethanedisulfonate,paraffin, etc.

The iminothiazoline compound (I) is useful as a herbicide to be employedfor paddy filed, crop field, orchards, pasture land, lawns, forests,non-agricultural fields, etc. Further, the iminothiazoline compound (I)may be also used together with any other herbicide to improve itsactivity as a herbicide, and in some cases, a synergistic effect can beexpected. Furthermore, it may be applied in combination with aninsecticide, an acaricide, a nematocide, a fungicide, a plant growthregulator, a fertilizer, a soil improver, etc.

The present invention will be explained more in detail by way ofPreparation Examples, Reference Examples, Formulation Examples and TestExamples, to which however the invention is not limited in any way.

Practical and presently preferred embodiments for production of theiminothiazoline compound (I) are illustratively shown in the followingexamples.

PREPARATION EXAMPLE 1 (Procedure (a))

A solution of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-bromomethylthiazolidine(0.7 g) and potassium t-butoxide (0.25 g) in t-butanol (30 ml) wasrefluxed for 5 hours. After removal of the solvent under reducedpressure, the concentrated residue was extracted with chlorofom (100ml), washed with water and dried over anhydrous magnesium sulfate. Thesolvent was removed under reduced pressure, and the residue wassubjected to column chromatography to give 0.36 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylthiazoline(Compound No. 1).

PREPARATION EXAMPLE 2 (Procedure (b))

A solution of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylenethiazolidine(2.0 g) and sodium methoxide (28% methanolic solution; 1.2 g) in ethanol(50 ml) was refluxed for 30 minutes. After removal of the solvent underreduced pressure, the concentrated residue was extracted with chlorofom(200 ml), washed with water and dried over anhydrous magnesium sulfate.The solvent was removed under reduced pressure, and the residue wassubjected to column chromatography to give 1.6 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylthiazoline(Compound No. 1).

PREPARATION EXAMPLE 3 (Procedure (c))

To a solution of 2-imino-3-(3-trifluoromethylphenyl)-5-ethylthiazoline(0.5 g) and triethylamine (0.6 g) in chloroform (30 ml), isovalerylchloride (0.8 g) was dropwise added under stirring at room temperature,and stirring was continued for 2 hours. After removal of the solventunder reduced pressure, the concentrated residue was extracted withethyl acetate (100 ml), washed with water and dried over anhydrousmagnesium sulfate. The solvent was removed under reduced pressure, andthe residue was subjected to column chromatography to give 0.2 g of2-isovalerylimino-3-(3-trifluoromethylphenyl)-5-ethylthiazoline(Compound No. 16).

PREPARATION EXAMPLE 4 (Procedure (c))

To a mixture of 2-imino-3-(3-trifluoromethylphenyl)-5-methylthiazolinehydrochloride (7.2 g) and triethylamine (7.4 g) in ethyl acetate (100ml), trifluoroacetic acid anhydride (5.2 g) was added under stirring atroom temperature, and stirring was continued for 3 hours. The residuewas washed with water and dried over anhydrous magnesium sulfate. Thesolvent was removed under reduced pressure to give a crystalline residuewhich was recrystallized from isopropanol to afford2-trifluoroacetylimino-3-(3-trifluoromethylphenyl)-5-methylthiazoline(Compound No. 54) (7.5 g). m.p., 128.1° C.

PREPARATION EXAMPLE 5 (Procedure (c))

A mixture of 2-imino-3-(3-trifluoromethylphenyl)-5-methylthiazolinehydrochloride (0.42 g), triethylamine (2.2 g),1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.8 g) anddifluoroacetic acid (0.75 g) in chloroform (10 ml) was refluxed for 8hours. The residue was Washed with aqueous hydrochloric acid and aqueouspotassium carbonate and dried over magnesium sulfate. The solvent wasremoved under reduced pressure, and the residue was subjected to columnchromatography to give2-difluoroacetylimino-3-(3-trifluoromethylphenyl)-5-methylthiazoline(Compound No. 63) (0.3 g). m.p., 117.9° C.

PREPARATION EXAMPLE 6 (Procedure (d))

A solution of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylthiazoline(1.0 g) and sodium methoxide (28% methanolic solution; 0.6 g) inmethanol (30 ml) was refluxed for 10 hours. After removal of thesolvent, the residue was extracted with chloroform (100 ml), washed withwater and dried over anhydrous magnesium. The solvent was removed underreduced pressure, and the residue was subjected to column chromatographyto give 0.8 g of2-methoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylthiazoline(Compound No. 3).

PREPARATION EXAMPLE 7 (Procedure (e))

A solution of2-(N-ethylcarbamoylimino)-3-(3-trifluoromethylphenyl)-5-methylenethiazolidine(0.2 g) and sodium methoxide (28% methanolic solution; 0.2 g ) inmethanol (30 ml) was refluxed for 10 hours. After removal of thesolvent, the residue was extracted with chloroform (100 ml), washed withwater and dried over anhydrous magnesium. The solvent was removed underreduced pressure, and the residue was subjected to column chromatographyto give 0.1 g of2-(N-ethylcarbamoylimino)-3-(3-trifluoromethylphenyl)-5-methylthiazoline(Compound No. 44).

PREPARATION EXAMPLE 8 (Procedure (f))

A solution of 2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)thiazolidine (1.6 g) and N-bromosuccinimide (2 g) in chloroform (50 ml)was refluxed for 10 hours. After cooling, the reaction mixture waswashed with an aqueous sodium sulfite solution and dried over anhydrousmagnesium sulfate. The solvent was removed under reduced pressure, andthe residue was subjected to column chromatography to give 0.9 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-bromothiazoline(Compound No. 30).

PREPARATION EXAMPLE 9 (Procedure (g))

A solution of 2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)thiazoline (0.5 g) and N-iodosuccinimide (0.4 g) in chloroform (30 ml)was refluxed for 20 hours. After cooling, the reaction mixture waswashed with an aqueous sodium sulfite solution and dried over anhydrousmagnesium sulfate. The solvent was removed under reduced pressure, andthe residue was subjected to column chromatography to give 0.1 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-iodothiazoline(Compound No. 42).

In the same manner as above, the iminothiazoline compounds (I) as shownin Table 6 were obtained.

                  TABLE 6                                                         ______________________________________                                         ##STR25##                     (I)                                            Compound                             Melting                                  No.     R.sup.1 R.sup.2 R.sup.3      point (°C.)                       ______________________________________                                        1       CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                                                   115.5                                    2       CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       CO.sub.2 C.sub.2 H.sub.5                                                                   97.1                                     3       CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 CH.sub.3                                                                          136.8                                    4       CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 (i)C.sub.3 H.sub.7                                                                126.0                                    5       CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       CO.sub.2 (i)C.sub.3 H.sub.7                                                                91.8                                     6       CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 (n)C.sub.3 H.sub.7                                                                91.1                                     7       CF.sub.3                                                                              CH.sub.3                                                                               ##STR26##   134.0                                    8       CF.sub.3                                                                              CH.sub.3                                                                               ##STR27##   155.7                                    9       CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                       103.0                                    10      CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 CH.sub.2 CHCH.sub.2                                                               99.1                                     11      CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                       101.6                                    12      CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 CH.sub.2 CCH                                                                      145.5                                    13      CF.sub.3                                                                              CH.sub.3                                                                              CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                       107.8                                    14      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       CO.sub.2 CH.sub.2 CCH                                                                      125.8                                    15      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       CO.sub.2 CH.sub.3                                                                          141.4                                    16      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       COCH.sub.2 CH(CH.sub.3).sub.2                                                              116.3                                    17      CF.sub.3                                                                              CH.sub.3                                                                               ##STR28##   132.6                                    18      CF.sub.3                                                                              CH.sub.3                                                                              COCH.sub.2 C(CH.sub.3).sub.3                                                               123.1                                    19      CF.sub.3 O                                                                            CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                                                   102.1                                    20      CF.sub.3 O                                                                            CH.sub.3                                                                              CO.sub.2 (i)C.sub.3 H.sub.7                                                                120.0                                    21      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                        ##STR29##   111.7                                    22      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       CO.sub.2 (n)C.sub.3 H.sub.7                                                                75.7                                     23      CF.sub.3                                                                              CH.sub.3                                                                              CO(i)C.sub.3 H.sub.7                                                                       139.6                                    24      CF.sub.3                                                                              CH.sub.3                                                                              CO(n)C.sub.4 H.sub.9                                                                       122.6                                    25      CF.sub.3 O                                                                            C.sub.2 H.sub.5                                                                       CO.sub.2 (i)C.sub.3 H.sub.7                                                                63.6                                     26      CF.sub.3                                                                              CH.sub.3                                                                               ##STR30##   100.3                                    27      CF.sub.3                                                                              CH.sub.3                                                                              COC(CH.sub.3).sub.3                                                                        94.7                                     28      CF.sub.3                                                                              CH.sub.3                                                                              COCH.sub.2 CH(CH.sub.3).sub.2                                                              92.4                                     29      CF.sub.3                                                                              CH.sub.3                                                                              COCH(CH.sub.3)CH.sub.2 CH.sub.3                                                            58.3                                     30      CF.sub.3                                                                              Br      COC.sub.2 C.sub.2 H.sub.5                                                                  136.8                                    31      CF.sub.3                                                                              Cl      CO.sub.2 C.sub.2 H.sub.5                                                                   138.2                                    32      CF.sub.3                                                                              Br      COC.sub.6 H.sub.5                                                                          182.4                                    33      CF.sub.3                                                                              Br      CO.sub.2 (i)C.sub.3 H.sub.7                                                                106.0                                    34      CF.sub.3                                                                              Br      CO.sub.2 CH.sub.3                                                                          106.8                                    35      CF.sub.3                                                                              Br      CO(n)C.sub.3 H.sub.7                                                                       141.4                                    36      CF.sub.3                                                                              Br      CO.sub.2 (n)C.sub.4 H.sub.9                                                                104.9                                    37      F       Br      CO.sub.2 C.sub.2 H.sub.5                                                                   172.4                                    38      Br      Br      CO.sub.2 C.sub.2 H.sub.5                                                                   155.4                                    39      Cl      Br      CO.sub.2 C.sub.2 H.sub.5                                                                   147.7                                    40      CF.sub.3                                                                              Br      CO.sub.2 C.sub.6 H.sub.5                                                                   137.7                                    41      CF.sub.3                                                                              Br      CO.sub.2 (n)C.sub.3 H.sub.7                                                                107.0                                    42      CF.sub.3                                                                              I       CO.sub.2 C.sub.2 H.sub.5                                                                   121.6                                    43      CF.sub.3                                                                              Br      CO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                          95.2                                     44      CF.sub.3                                                                              CH.sub.3                                                                              CONHC.sub.2 H.sub.5                                                                        93.2                                     45      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       SO.sub.2 CF.sub.3                                                                          115.5                                    46      CF.sub.3                                                                              CH.sub.3                                                                              COCH.sub.2 CH.sub.2 Cl                                                                     155.2                                    47      CF.sub.3                                                                              CH.sub.3                                                                              COC.sub.2 H.sub.5                                                                          164.6                                    48      CF.sub.3                                                                              CH.sub.3                                                                              COC.sub.3 H.sub.7                                                                          111.0                                    49      CF.sub.3                                                                              CH.sub.3                                                                              COCH.sub.2 C.sub.6 H.sub.5                                                                 126.4                                    50      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       COCH.sub.3   87.8                                     51      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       COC.sub.2 H.sub.5                                                                          117.5                                    52      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       CO(n)C.sub.3 H.sub.7                                                                       119.0                                    53      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       CO(i)C.sub.3 H.sub.7                                                                       96.6                                     54      CF.sub.3                                                                              CH.sub.3                                                                              COCF.sub.3   128.1                                    55      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       COCF.sub.3   92.0                                     56      CF.sub.3                                                                              Br      COCF.sub.3   113.2                                    57      CF.sub.3                                                                              CH.sub.3                                                                              COC.sub.2 F.sub.5                                                                          98.5                                     58      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       COC.sub.2 F.sub.5                                                                          94.1                                     59      CF.sub.3                                                                              CH.sub.3                                                                              COC.sub.3 F.sub.7                                                                          61.7                                     60      CF.sub.3 O                                                                            CH.sub.3                                                                              COCH.sub.3   150.8                                    61      CF.sub.3 O                                                                            CH.sub.3                                                                              COCF.sub. 3  104.7                                    62      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                        ##STR31##   98.3                                     63      CF.sub.2                                                                              CH.sub.3                                                                              COCHF.sub.2  117.9                                    64      CF.sub.3                                                                              CH.sub.3                                                                              COCH.sub.2 F 135.7                                    65      CF.sub.3                                                                              C.sub.2 H.sub.5                                                                       COCHF.sub.2  96.3                                     ______________________________________                                    

Practical embodiments for preparation of various starting compounds andintermediates are shown in the following examples.

Compound (III): PREPARATION EXAMPLE 8

A mixture of 3-trifluoromethylaniline (30 g) and propargyl bromide (12g) was stirred at 80° C. for 3 hours, followed by filtration of thereaction mixture. The filtrate was subjected to column chromatography togive N-propargyl-3-trifluoromethylaniline (7 g). A solution ofN-propargyl-3-trifluoromethylaniline thus obtained (5.1 g) andethoxycarbonyl isothiocyalate (3.7 g) in tetrahydrofuran (100 ml) wasstirred at room temperature for 8 hours, and the solvent was removedunder reduced pressure. The concentrated residue was extracted withchloroform (200 ml), washed with water and dried over anhydrousmagnesium sulfate. After removal of the solvent, the residue wassubjected to column chromatography to give 5.7 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylenethiazolidine (Compound (i)).

PREPARATION EXAMPLE 9

A solution of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-bromomethylthiazolidine(0.7 g) and potassium t-butoxide (0.25 g) in t-butanol (30 ml) wasrefluxed for 5 hours, and the solvent was distilled off under reducedpressure. The residue was extracted with chloroform (100 ml), washedwith water and dried over anhydrous magnesium sulfate. After removal ofthe solvent, the residue was subjected to column chromatography to give0.25 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylenethiazolidine(Compound (i)).

PREPARATION EXAMPLE 10

A solution of 2-imino-3-(3-trifluoromethylphenyl)-5-methylenethiazoline(0.5 g), triethylamine (0.3 g) and ethyl chlorocarbonate (0.5 g) intetrahydrofuran (30 ml) was stirred at room temperature for 24 hours,followed by removal of the solvent under reduced pressure. The residuewas extracted with ethyl acetate (100 ml), washed with water and driedover anhydrous magnesium sulfate. After removal of the solvent, theresidue was subjected to column chromatography to give 0.2 g of2-ethoxycarbonylimino-3(3-trifluoromethylphenyl)-5-methylenethiazoline(Compound (i)).

In the same manner as above, the compounds (III) as shown in Table 7were obtained.

                  TABLE 7                                                         ______________________________________                                         ##STR32##                    (III)                                           Compound                            Melting                                   No.      R.sup.1 R.sup.4 R.sup.5    point (°C.)                        ______________________________________                                        i        CF.sub.3                                                                              H       OC.sub.2 H.sub.5                                                                         97.2                                      ii       CF.sub.3                                                                              CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         137.2                                     iii      CF.sub.3                                                                              CH.sub.3                                                                              O(i)C.sub.3 H.sub.7                                                                      128.9                                     iv       CF.sub.3                                                                              H                                                                                      ##STR33## 129.9                                     v        CF.sub.3                                                                              H       CH.sub.2 C(CH.sub.3).sub.3                                                               103.2                                     vi       CF.sub.3                                                                              H       (i)C.sub.3 H.sub.7                                                                       97.8                                      vii      CF.sub.3                                                                              H       OC.sub.6 H.sub.5                                                                         133.5                                     viii     CF.sub.3                                                                              H       CH.sub.2 CH.sub.2 Cl                                                                     74.2                                      ______________________________________                                    

Compound (XI): PREPARATION EXAMPLE 11

To a solution of N-cyano-3-trifluoromethylaniline (5.0 g) in acetone(100 ml), potassium carbonate (7.4 g) and propargyl bromide (3.5 g) wereadded, and the resultant mixture was stirred at room temperature for 10hours, followed by filtration of the reaction mixture. The solvent wasremoved from the filtrate by distillation under reduced pressure, andthe residue was subjected to column chromatography to giveN-cyano-N-propargyl-3-trifluoromethylaniline (3.8 g). The thus obtainedN-cyano-N-propargyl-3-trifluoromethylaniline (1 g) and a catalyticamount of triethylamine were dissolved in methanol (30 ml), and theresultant mixture was cooled to 0° C. Hydrogen sulfide was graduallyintroduced into the mixture for 20 minutes while keeping the temperatureat 0° C., followed by introduction of nitrogen gas to remove hydrogensulfide. The solvent was removed by distillation, and the residue wassubjected to column chromatography to give 0.2 g of2-imino-3-(3-trifluoromethylphenyl)-5-methylenethiazolidine (Compound(ix)).

In the same manner as above, the compound (XI) as shown in Table 8 wasobtained.

                  TABLE 8                                                         ______________________________________                                         ##STR34##                    (XI)                                            Compound No. R.sup.1                                                                              R.sup.4  .sup.1 H-NMR (δ)                           ______________________________________                                        ix           CF.sub.3                                                                             H        7.2-7.9(4H), 6.4(1H),                                                         5.0-5.2(2H), 4.7(2H)                             ______________________________________                                    

Compound (IV): PREPARATION EXAMPLE 12

A mixture of2-(t-butoxycarbonylimino)-3-(3-trifluoromethylphenyl)-5-ethylthiazoline(1 g) and trifluoroacetic acid (3 g) in chloroform (20 ml) was stirredat room temperature for 3 hours, followed by addition of water (50 ml)thereto. The resultant mixture was neutralized with potassium carbonate,extracted with chloroform and dried over anhydrous magnesium sulfate.The solvent was removed by distillation under reduced pressure, and theresidue was subjected to column chromatography to give 0.3 g of2-imino-3-(3-trifluoromethylphenyl)-5-ethylthiazoline (Compound (x)).

PREPARATION EXAMPLE 13

A mixture of2-(acetylimino)-3-(3-trifluoromethylphenyl)-5-methylthiazoline (1 g) andhydrochloric acid (38%, 4 ml) in ethanol-water (1 : 2, 15 ml) wasrefluxed for 3 hours. Ethanol was removed by distillation under reducedpressure, and the residue was neutralized with potassium carbonate,extracted with ethyl acetate and dried over anhydrous magnesium sulfate.The solvenet was removed by distillation under reduced pressure to give0.4 g of 2-imino-3-(3-trifluoromethylphenyl)-5-methylthiazoline(Compound (xi)).

In the same manner as above, the compound (IV) as shown in Table 9 wasobtained.

                  TABLE 9                                                         ______________________________________                                         ##STR35##                    (IV)                                            Compound No. R.sup.1                                                                              R.sup.4  .sup.1 H-NMR (δ)                           ______________________________________                                        x            CF.sub.3                                                                             CH.sub.3 7.5-7.9(4H), 6.4(1H),                                                         5.3(1H), 2.5(q. 2H),                                                          1.25(t, 3H)                                      xi           CF.sub.3                                                                             H        7.4-7.9(5H),                                                                  6.4(1H), 2.1(3H)                                 ______________________________________                                    

Compound (VIII): PREPARATION EXAMPLE 14

A solution of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-bromothiazoline (4.7g), tributyltin hydride (6.9 g) and a catalytic amount of benzoylperoxide in tetrahydrofuran (100 ml) was refluxed for 10 hours. Thesolvent was removed by distillation, and the residue was washed withhexane. Recrystallization from a mixture of hexane and ethanol gave 2.85g of 2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)thiazoline(Compound (xii)).

In the same manner as above, the compound (VIII) as shown in Table 10was obtained.

                  TABLE 10                                                        ______________________________________                                         ##STR36##                   (VIII)                                           Compound No.                                                                              R.sup.7  R.sup.8 Melting point (°C.)                       ______________________________________                                        xii         CF.sub.3 OC.sub.2 H.sub.5                                                                      134.5                                            ______________________________________                                    

Compound (II): Reference Example 1

A solution of N-allyl-3-trifluoromethylanilien (3 g) and ethoxycarbonylisothiocyanate (2.1 g) in chloroform (50 ml) was stirred at roomtemperature for 3 hours, followed by removal of the solvent. The residuewas subjected to column chromatography to giveN-allyl-N-(3-trifluoromethylphenyl)-N'-ethoxycarbonylthiourea (3.5 g).The thus obtained thiourea (1 g) and N-bromosuccinimide (0.6 g) weredissolved in chloroform (50 ml), and the solution was stirred at roomtemperature for 6 hours. The solvent was removed by distillation, andthe residue was extracted with ethyl ether. The extract was washed withan aqueous sodium sulfite solution and an aqueous sodium hydroxidesolution in order, dried over anhydrous magnesium sulfate andconcentrated under reduced pressure to give 1.2 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-bromomethylthiazolidine.m.p., 108.3° C.

Reference Example 2

A solution ofN-crotyl-N-(3-trifluoromethylphenyl)-N'-ethoxycarbonylthiourea (6 g) andsodium methoxide (28% methanolic solution; 6.6 g) in methanol (100 ml)was refluxed for 2 days. After removal of the solvent, the residue wasextracted with chloroform, washed with water and dried over anhydrousmagnesium sulfate. The solvent was removed under reduced pressure, andthe residue was subjected to column chromatography to giveN-crotyl-N-(3-trifluoromethylphenyl)thiourea (2.4 g). The thus obtainedthiourea (2.0 g) and N-bromosuccinimide (1.4 g) were dissolved inchloroform (50 ml), and the resultant solution was stirred at roomtemperature for 5 hours, washed with an aqueous sodium sulfite solutionand dried over anhydrous magnesium sulfate. After removal of the solventby distillation under reduced pressure, the residue was subjected tocolumn chromatography to give 0.8 g of2-imino-3-(3-trifluoromethylphenyl)-5-(1-bromoethyl)thiazolidine.

The above obtained2-imino-3-(3-trifluoromethylphenyl)-5-(1-bromoethyl)thiazolidine (0.8 g)and triethylamine (1 g) were dissolved in tetrahydrofuran (50 ml),followed by dropwise addition of isopropyl chlorocarbonate (0.5 g). Theresultant mixture was stirred at room temperature for 3 hours. Thesolvent was removed by distillation under reduced pressure. The residuewas extracted with chloroform, washed with water and dried overanhydrous magnesium sulfate. After removal of the solvent, the residuewas subjected to column chromatography to give 0.1 g of2-isopropyloxycarbonylimino-3-(3-trifluoromethylphenyl)-5-(1-bromoethyl)thiazolidine.

Compound (VI): Reference Example 3

To a solution of2-phenoxycarbonylimino-3-(3-trifluoromethylphenyl)-5-methylenethiazolidine(0.5 g) in diethyl ether (30 ml), 70% ethylamine (10 ml) was added, andthe resultant mixture was stirred at room temperature for 5 hours. Thereaction mixture was extracted with diethyl ether. The extract waswashed with water, dried over anhydrous magnesium sulfate andconcentrated under reduced pressure. The residue was subjected to columnchromatography to give 0.23 g of2-(N-ethylcarbamoyl)-3-(3-trifluoromethylphenyl)-5-methylenethiazolidine.m.p., 118.5° C.

Compound (VII): Reference Example 4

A solution of N-(3-trifluoromethylphenyl)thiourea (6.1 g), dibromoethane(5.7 g) and anhydrous potassium carbonate (11.5 g) in acetone (60 ml)was refluxed for 1 day. The solvent was removed by distillationtherefrom, and the residue was extracted with ethyl ether, washed withwater, dried over anhydrous magnesium sulfate and subjected to columnchromatography to give 7.5 g of2-imino-3-(3-trifluoromethylphenyl)thiazolidine. The thus obtained2-imino-3- (3-trifluoromethylphenyl) thiazolidine (1.0 g), n-butylchlorocarbonate (0.61 g) and triethylamine (1.2 g) were dissolved intetrahydrofuran, and the resultant solution was stirred at roomteperature for 5 hours. The solvent was removed, and the residue wasextracted with ethyl acetate, washed with water and dried over anhydrousmagnesium sulfate. After removal of the solvent, the residue wassubjected to column chromatography to give 0.57 g of2-butoxycarbonylimino-3-(3-trifluoromethylphenyl)thiazolidine.

Reference Example 5

A solution of N-(3-trifluoromethylphenyl)-N'-ethoxycarbonylthiourea (1.8g), dibromoethane (1.29 g) and anhydrous potassium carbonate (2.6 g) inacetone (20 ml) was refluxed for 5 hours. The solvent was removed bydistillation, and the residue was extracted with diethyl ether. Theextract was washed with water, dried over anhydrous magnesium sulfateand concentrated under reduced pressure. The residue was recrystallizedfrom a mixture of hexane and ethanol to give 1.63 g of2-ethoxycarbonylimino-3-(3-trifluoromethylphenyl)thiazolidine. m.p.,75.8° C.

Practical embodiments of the herbicidal composition according to theinvention are illustratively shown below wherein parts are by weight.The compound number of the active ingredient corresponds to the one inTable 6.

Formulation Example 1

Fifty parts of any one of Compound Nos. 1 to 65, 3 parts of calciumligninsulfonate, 2 parts of sodium laurylsulfate and 45 parts ofsynthetic hydrous silica are well mixed while being powdered to obtainwettable powder.

Formulation Example 2

Five parts of any one of Compound No. 1 to 65, 15 parts of "ToxanoneP8L®" (a commercial surface active agent; Sanyo Kasei K.K.) and 80 partsof cyclohexanone are well mixed to obtain emulsifiable concentrate.

Formulation Example 3

Two parts of any one of Compound No. 1 to 65, 1 part of synthetichydrous silica, 2 parts of calcium ligninsulfonate, 30 parts ofbentonite and 65 parts of kaolin clay are well mixed while beingpowdered. The mixture is then kneaded with water, granulated and driedto obtain granules.

Formulation Example 4

Twenty-five parts of any one of Compound No. 1 to 65 are mixed with 3parts of polyoxyethylene sorbitan monooleate, 3 parts of carboxymethylcellulose (CMC) and 69 parts of water and pulverized until the particlesize of the mixture becomes less than 5 microns to obtain a suspension.

The biological data of the iminothiazoline compound (I) as the herbicidewill be illustratively shown in the following Test Examples wherein thephytotoxicity to crop plants and the herbicidal activity on weeds wereobserved visually as to the degree of germination as well as the growthinhibition and rated with an index 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10,the numeral "0" indicating no material difference as seen in comparisonwith the untreated plants and the numeral "10" indicating the completeinhibition or death of the test plants. The compound number in thebiological data corresponds to the one in Table 6.

The compounds as shown in Table 11 were used for comparison.

                  TABLE 11                                                        ______________________________________                                        Com-                                                                          pound                                                                         No.   Structure              Remarks                                          ______________________________________                                        (A)                                                                                  ##STR37##             Benthiocarb (commercial herbicide)               (B)                                                                                  ##STR38##             EP-A-0349282                                     (C)                                                                                  ##STR39##             EP-A-0349282                                     (D)                                                                                  ##STR40##             EP-A-0349282                                     (E)                                                                                  ##STR41##             EP-A-0349282                                     (F)                                                                                  ##STR42##             EP-A-0349282                                     (G)                                                                                  ##STR43##             EP-A-0349282                                     (H)                                                                                  ##STR44##             EP-A-0349282                                     (I)                                                                                  ##STR45##             EP-A-0349282                                     (J)                                                                                  ##STR46##             EP-A-0349282                                     ______________________________________                                    

Test Example 1

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of japanese millet, tallmorningglory and velvetleaf were sowed therein and covered with soil. Adesignated amount of the test compound formulated in an emulsifiableconcentrate as in Formulation Example 2 was diluted with water; and thedilution was sprayed onto the soil surface by means of a small handsprayer at a spray volume of 1,000 liters per hectare. The test plantswere grown in a greenhouse for 20 days, and the herbicidal activity wasexamined. The results are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                                     Herbicidal activity                                                                           Tall                                             Compound                                                                              Dosage     Japanese  morning-                                                                              Velvet-                                  No.     (g/ha)     millet    glory   leaf                                     ______________________________________                                        1       2000       9         9       10                                               500        9         7       9                                        2       2000       9         10      10                                               500        7         7       7                                        3       2000       10        9       10                                               500        9         7       8                                        4       2000       10        10      10                                               500        10        10      10                                               125        10        10      8                                        5       2000       10        10      10                                               500        9         10      8                                                125        8         9       --                                       6       2000       10        10      10                                               500        10        10      --                                       7       2000       9         10      10                                               500        9         8       --                                       8       2000       8         9       --                                               500        7         8       --                                       9       2000       10        10      10                                               500        10        10      --                                       10      2000       10        10      10                                               500        10        7       --                                       11      2000       10        10      9                                                500        10        9       --                                       12      2000       10        10      10                                               500        10        7       8                                        13      2000       10        10      10                                       14      2000       9         9       10                                       15      2000       10        9       10                                       16      2000       10        10      9                                                500        10        10      9                                        17      2000       10        10      10                                               500        10        10      --                                       18      2000       10        10      10                                               500        9         9       --                                       19      2000       10        9       7                                                500        10        8       --                                       20      2000       10        10      10                                               500        10        10      10                                       21      2000       10        10      --                                               500        10        10      --                                       22      2000       10        10      --                                               500        10        7       --                                       23      2000       10        10      10                                               500        10        9       10                                       24      2000       10        9       --                                               500        10        9       --                                       25      2000       10        10      10                                               500        10        9       9                                                125        9         9       8                                        26      2000       10        10      10                                               500        10        10      10                                               125        9         9       8                                        27      2000       10        10      --                                               500        9         9       --                                       28      2000       10        10      8                                                500        10        10      7                                        29      2000       10        10      8                                                500        10        9       7                                        30      2000       9         10      10                                               500        9         --      10                                       31      2000       9         7       8                                                500        9         --      7                                        32      2000       7          7      9                                        33      2000       9         10      9                                                500        9         10      7                                        34      2000       10        10      10                                               500        9         8       10                                       35      2000       10        10      --                                       36      2000       9         10      7                                                500        7         8       --                                       40      2000       --        10      10                                       41      2000       10        10      10                                               500        10        10      10                                               125        7         8       7                                        42      2000       9         10      10                                               500        8         9       10                                       46      2000       10        10      9                                                500        10        7       7                                        47      2000       10        10      10                                               500        10        8       7                                        48      2000       10        10      10                                               500        10        10      --                                       49      2000       9         10      10                                               500        9         10      9                                        50      2000       10        10      10                                               500        10        10      9                                        51      2000       10        10      10                                               500        10        10      9                                        52      2000       10        10      10                                               500        10        10      9                                        53      500        10        10      9                                        54      500        10        10      10                                               125        10        10      10                                       55      500        10        10      10                                               125        10        10      10                                       56      500        9         9       9                                                125        8         8       8                                        57      500        9         10      9                                        58      500        10        10      8                                                125        9         7       7                                        59      2000       7         9       9                                        60      500        10        10      10                                       61      500        10        10      10                                               125        9         10      7                                        62      2000       10        10      9                                        63      500        10        10      10                                               125        10        10      10                                       64      500        10        10      10                                               125        9         9       7                                        65      500        10        10      10                                               125        9         10      10                                       A       2000       7         0       0                                                500        0         0       0                                        B       2000       0         0       0                                        C       2000       0         2       4                                                500        0         0       0                                        D       2000       0         0       0                                        E       2000       5         5       5                                                500        0         3       0                                        F       2000       7         1       3                                                500        5         0       3                                        ______________________________________                                    

Test Example 2

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of japanese millet, morningglory,radish and velvetleaf were sowed therein and cultivated in a greenhousefor 10 days. A designated amount of the test compound formulated in anemulsifiable concentrate as in Formulation Example 2 was diluted withwater containing a spreading agent, and the dilution was sprayed overthe foliage of the test plant by means of a small hand sprayer at aspray volume of 1,000 liters per hectare. The test plants were furthergrown in the greenhouse for 20 days, and the herbicidal activity wasexamined. The results are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                                   Herbicidal activity                                                Compound                                                                              Dosage   Japanese Morning-      Velvet-                               No.     (g/ha)   millet   glory  Radish leaf                                  ______________________________________                                        1       2000     9        9      10     9                                             500      9        9      10     8                                     2       2000     9        10     10     9                                             500      9        10     10     7                                     3       2000     9        10     10     10                                            500      9        9      10     --                                    4       2000     10       10     10     10                                            500      9        10     10     10                                            125      8        10     10     7                                     5       2000     9        10     10     10                                            500      9        10     10     10                                            125      9        10     9      7                                     6       2000     9        10     10     10                                            500      9        10     10     8                                             125      9        10     10     7                                     7       2000     8        10     10     9                                             500      8        10     8      9                                     8       2000     --       10     8      10                                    9       2000     9        10     10     8                                             500      8        10     10     --                                    10      2000     9        10     10     9                                             500      9        10     10     --                                    11      2000     9        10     10     10                                            500      9        10     10     8                                     12      2000     9        10     10     10                                            500      9        10     10     10                                            125      7        10     10     7                                     13      2000     9        10     10     10                                            500      9        10     10     9                                             125      7        9      10     7                                     14      2000     8        10     10     10                                    15      2000     7        7      10     8                                     16      2000     9        10     10     9                                             500      9        10     10     8                                     17      2000     9        10     10     9                                             500      9        10     10     9                                             125      8        10     9      8                                     18      2000     9        10     10     10                                            500      9        10     10     10                                            125      7        9      10     10                                    19      2000     9        10     7      7                                     20      2000     10       10     10     9                                             500      9        9      9      8                                     21      2000     9        10     10     10                                            500      9        10     9      10                                            125      9        9      8      10                                    22      2000     9        10     10     8                                             500      9        10     10     7                                     23      2000     10       10     10     10                                            500      9        10     10     10                                            125      9        9      10     9                                     24      2000     10       10     10     9                                             500      9        10     10     8                                             125      9        9      10     8                                     25      2000     10       10     10     10                                            500      9        10     10     9                                             125      9        10     9      9                                     26      2000     9        10     10     10                                            500      9        10     10     10                                            125      9        10     10     10                                    27      2000     10       10     10     10                                            500      9        10     10     9                                             125      7        10     10     9                                     28      2000     10       10     10     9                                             500      9        10     9      9                                             125      9        10     9      8                                     29      2000     9        10     10     9                                             500      9        10     9      9                                             125      8        10     9      7                                     30      2000     9        9      10     9                                             500      9        9      10     9                                             125      9        9      10     8                                     31      2000     10       10     10     10                                            500      10       10     10     10                                            125      9        10     10     10                                    32      2000     --       9      --     8                                     33      2000     9        10     10     10                                            500      9        10     10     10                                            125      9        10     10     9                                     34      2000     9        10     10     10                                            500      9        9      10     10                                            125      9        9      10     10                                    35      2000     9        10     10     9                                             500      9        10     10     8                                             125      8        10     10     8                                     36      2000     9        10     10     10                                            500      9        10     10     10                                            125      7        10     10     10                                    38      2000     --       8      10     9                                     39      2000     --       9      7      --                                    41      2000     10       10     10     10                                            500      9        10     10     10                                            125      9        10     10     10                                    42      2000     10       10     10     10                                            500      --       10     10     10                                    43      2000     --       10     10     10                                            500      --       10     10     10                                    44      2000     --       9      7      --                                    45      2000     --       10     10     8                                     46      2000     9        9      9      9                                             500      9        9      9      9                                     47      2000     9        10     10     9                                             500      9        10     10     9                                     48      2000     9        10     10     9                                             500      9        10     10     9                                             125      9        10     10     7                                     49      2000     9        10     10     9                                             500      8        10     10     9                                             125      7        10     10     9                                     50      2000     10       10     10     9                                             500      10       10     10     9                                     51      2000     10       10     10     10                                            500      10       10     10     9                                     52      2000     10       10     10     10                                            500      10       10     10     9                                     53      500      10       10     10     9                                     54      500      9        10     10     9                                             125      9        10     10     9                                     55      500      10       10     10     10                                            125      10       10     10     10                                    56      500      9        10     10     9                                             125      7        10     9      9                                     57      500      9        10     10     9                                             125      9        10     10     9                                     58      500      9        10     10     9                                             125      8        10     10     9                                     59      2000     8        10     10     9                                     60      500      9        9      9      7                                     61      500      9        9      9      10                                            125      9        9      9      10                                    62      500      9        10     10     10                                            125      9        10     10     9                                     63      500      9        10     10     10                                            125      9        10     10     10                                    64      500      9        10     10     10                                            125      7        10     9      7                                     65      500      10       9      10     10                                            125      10       9      10     10                                    A       2000     9        2      1      0                                             500      3        1      0      0                                     B       2000     1        3      0      0                                             500      0        1      0      0                                     C       2000     3        6      3      4                                             500      0        6      0      1                                     D       2000     0        2      1      0                                             500      0        1      0      0                                     E       2000     3        6      2      1                                             500      0        3      1      0                                     F       2000     6        2      5      4                                             500      1        0      2      0                                     ______________________________________                                    

Test Example 3

Cylindrical plastic pots (diameter, 8 cm; height, 12 cm) were filledwith paddy field soil, and the seeds of barnyardgrass (Echinochloaoryzicola) and hardstem bulrush (Scirpus juncoides) were sowed in 1 to 2cm depth. Water was poured therein to make a flooded condition, and riceseedlings of 2-leaf stage were transplanted therein, and the test plantswere grown in a greenhouse. Six days (at that time seeds began togerminate) thereafter, a designated amount of the test compoundformulated in an emulsifiable concentrate as in Formulation Example 2and diluted with water (2.5 ml) was applied to the pots by perfusion.The test plants were grown for an additional 19 days in the greenhouse,and the herbicidal activity and phytotoxicity were examined. The resultsare shown in Table 14.

                  TABLE 14                                                        ______________________________________                                                           Herbicidal activity                                        Compound                                                                              Dosage    Phytotoxicity                                                                            Barnyard-                                                                             Hardstem                                 No.     (g/ha)    Rice plant grass   bulrush                                  ______________________________________                                        1       63        1          8       7                                        2       250       1          10      9                                                63        1          10      --                                       4       63        1          9       8                                        5       63        1          10      8                                                16        1          10      8                                        6       63        1          8       --                                       7       63        1          10      8                                                16        1          9       --                                       8       63        1          9       --                                       9       63        1          9       9                                        10      63        1          10      7                                        11      63        1          8       --                                       12      16        1          10      8                                        13      63        1          9       7                                        14      63        1          7       8                                        15      250       1          10      9                                                63        0          7       --                                       16      63        1          10      7                                        17      63        1          10      9                                        18      63        1          9       --                                       19      250       1          10      10                                               63        0          9       8                                        20      63        1          10      --                                       21      63        1          10      --                                               16        1          10      7                                        22      63        1          10      8                                                16        1          10      7                                        23      63        1          10      9                                        24      63        1          9       9                                                16        0          8       9                                        25      63        1          9       9                                        26      63        1          10      9                                                16        1          9       9                                        27      63        1          10      --                                       28      63        1          8       8                                        30      250       0          10      10                                               63        0          9       8                                        31      250       0          9       9                                                63        0          9       8                                        33      63        1          9       7                                        34      63        1          9       8                                        35      250       1          9       9                                        36      250       1          10      9                                        41      250       1          10      9                                        42      63        1          9       8                                        43      250       1          9       --                                       46      63        1          9       9                                                16        0          9       7                                        48      63        1          10      10                                               16        1          9       9                                        49      63        1          9       8                                                16        0          8       7                                        51      63        1          10      8                                        54      16        0          10      7                                        55      16        1          10      --                                       57      63        1          10      7                                        58      63        1          10      7                                        62      63        1          8       --                                       63      16        0          9       8                                        64      250       1          10      9                                        65      16        1          8       8                                        A       250       0          7       3                                                63        0          2       0                                                16        0          0       0                                        B       250       0          0       0                                        C       250       0          0       0                                        D       250       0          0       0                                        E       250       0          0       0                                        F       250       0          1       1                                        ______________________________________                                    

Test Example 4

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of catchweed bedstraw, common chickweed, persian speedwell, fieldpansy and wheat were sowed therein in 1 to 2 cm depth. A designatedamount of the test compound formulated in a wettable powder as inFormulation Example 1 was diluted with water, and the dilution wassprayed onto the soil surface by means of a small hand sprayer at aspray volume of 1,000 liters per hectare. The test plants were grown ina greenhouse for 20 days, and the herbicidal activity and phytotoxicitywere examined. The results are shown in Table 15.

                  TABLE 15                                                        ______________________________________                                                     Herbicidal activity                                              Com-           Phyto-  Catch- Common Persian                                  pound Dosage   toxicity                                                                              weed   chick- speed-                                                                              Field                              No.   (g/ha)   Wheat   bedstraw                                                                             weed   well  pansy                              ______________________________________                                        1     500      0       9      10     10    10                                 2     500      0       8      10     10    --                                 4     500      1       9      10     10    10                                 30    2000     0       9      10     10    10                                 31    2000     1       9      10     10    10                                 33    2000     0       9      10     10    10                                       500      0       7      10     10    10                                 34    500      0       9      10     10    10                                 35    500      0       7      10     10    10                                 36    500      1       7      10     10    10                                 46    125      0       9      8      10    8                                  52    500      1       7      10     10    8                                  A     2000     0       0      0      10    10                                 G     2000     0       0      3      10    2                                        500      0       0      0       8    0                                  ______________________________________                                    

Test Example 5

vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of common chickweed, persian speedwell, blackgrass, annualbluegrass, wheat and barley were sowed therein in 1 to 2 cm depth. Adesignated amount of the test compound formulation in an emulsifiableconcentrate as in Formulation Example 2 was diluted with water, and thedilution was sprayed onto the soil surface by means of an automaticsprayer at a spray volume of 1,000 liters per hectare. The test plantswere grown in a greenhouse for 25 days, and the herbicidal activity andphytotoxicity were examined. The results are shown in Table 16.

                                      TABLE 16                                    __________________________________________________________________________                        Herbicidal activity                                       Com-      Phyto-    Common                                                                             Persian   Annual                                     pound                                                                              Dosage                                                                             toxicity  chick-                                                                             speed-                                                                             Black-                                                                             blue-                                      No.  (g/ha)                                                                             Wheat                                                                              Barley                                                                             weed well grass                                                                              grass                                      __________________________________________________________________________    3    125  0    1    10   10   8    9                                          4    500  1    1    10   10   10   10                                              125  0    0    10   10   9    10                                         5    125  0    1    10   10   9    10                                         6    125  0    1    10   10   9    --                                         7    500  0    1    10   10   10   10                                              125  0    0    10   8    7    9                                          9    125  --   1    10   10   7    10                                         10   125  --   0    10   10   10   10                                         12   125  0    1    9    7    7    8                                          14   500  1    1    10   10   7    10                                         17   500  0    1    10   10   10   10                                              125  0    0    9    10   8    10                                         20   500  --   0    10   10   10   10                                              125  1    0    --   10   7    8                                          21   500  0    --   10   10   10   10                                              125  0    0    10   10   9    10                                         22   500  0    1    7    10   --   10                                              125  0    0    7    10   --   8                                          23   125  0    0    10   10   9    10                                         24   125  0    1    --   10   9    10                                         26   500  0    --   9    10   9    10                                              125  0    0    --   10   8    10                                         28   125  0    0    7    10   8    10                                         30   500  0    --   10   10   10   10                                              125  0    0    10   10   --   8                                          33   500  1    --   10   10   9    9                                               125  0    1    10   10   8    9                                          35   125  0    --   9    10   10   9                                          41   500  0    --   10   10   10   10                                              125  0    1    9    10   10   10                                         G    125  0    0    0    6    0    0                                          H    500  0    0    1    5    2    0                                               125  0    0    0    5    0    0                                          I    125  0    0    6    6    2    4                                          J    125  0    0    0    6    0    0                                          __________________________________________________________________________

Test Example 6

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of soybean, cotton, corn, rice plant, velvetleaf and green foxtailwere sowed 1 to 2 cm depth. A designated amount of the test compoundformulated in a wettable powder as in Formulation Example 1 was dilutedwith water, and the dilution was sprayed onto the soil surface by meansof a small hand sprayer at a spray volume of 1000 liters per hectare.The test plants were grown in a greenhouse for 20 days, and theherbicidal activity and phytotoxicity were examined. The results areshown in Table 17.

                  TABLE 17                                                        ______________________________________                                                Phytotoxicity  Herbicidal activity                                    Com-                                                                          pound Dosage  Soy-              Rice Velvet-                                                                              Green                             No.   (g/ha)  bean   Cotton                                                                              Corn plant                                                                              leaf   foxtail                           ______________________________________                                        30    500     1      0     0    0    9      10                                A     500     1      0     1    1    0      6                                 G     500     0      0     0    0    0      0                                 ______________________________________                                    

Test Example 7

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of cotton, black nightshade, johnsongrass, green foxtail weresowed therein 1 to 2 cm depth. A designated amount of the test compoundformulated in an emulsifiable concentrate as in Formulation Example 2was diluted with water, and the dilution was sprayed onto the soilsurface by means of a small hand sprayer at a spray volume of 1,000liters per hectare. The test plants were grown in a greenhouse for 20days, and the herbicidal activity and phytotoxicity were examined. Theresults are shown in Table 18.

                  TABLE 18                                                        ______________________________________                                                        Herbicidal activity                                                            Phyto-   Black  Barn-  Green                                 Compound                                                                              Dosage   toxicity night- yard-  fox-                                  No.     (g/ha)   Cotton   shade  grass  tail                                  ______________________________________                                        1       500      0        10     9      10                                    2       500      0        10     --     10                                    3       500      0        10     8      10                                    4       500      0        10     10     10                                    5       500      1        10     10     10                                    6       500      0        10     10     10                                    7       500      1        10     10     9                                     8       500      0        --     7      9                                     9       500      0        10     10     9                                     10      500      0        10     10     10                                    11      500      0        10     10     10                                    12      500      1        10     7      10                                    13      500      0        10     10     10                                    14      500      0        10     8      10                                    17      500      1        9      10     10                                    18      500      0        9      9      9                                     19      500      1        8      7      9                                     20      500      0        9      10     9                                     21      500      0        8      10     9                                     23      500      0        9      10     9                                     25      500      1        7      10     10                                    26      500      1        7      10     9                                     29      500      0        10     10     9                                     30      500      0        9      10     10                                    31      500      1        10     9      10                                    33      500      1        --     10     10                                    34      500      0        10     9      10                                    46      500      0        10     9      10                                    48      500      1        10     10     9                                     49      500      1        10     8      10                                    50      500      0        10     10     8                                     51      500      0        9      10     10                                    52      500      0        9      10     10                                    53      500      0        9      10     10                                            125      0        8      10     10                                    54      500      1        10     10     10                                            125      0        9      10     10                                    55      125      0        10     9      10                                    57      500      1        10     10     10                                    58      125      0        10     7      9                                     62      500      0        10     8      9                                     63      500      1        10     10     10                                            125      0        10     9      10                                    64      500      0        10     10     10                                            125      0        10     8      10                                    A       500      0        0      6      6                                     G       500      0        0      0      0                                     H       500      0        1      1      1                                     I       500      1        0      2      --                                    J       500      0        0      1      4                                     ______________________________________                                    

Test Example 8

Vats (33 cm×23cm×11 cm) were filled with upland field soil, and theseeds of soybean, corn, rice plant and barnyardgrass were sowed therein1 to 2 cm depth. A designated amount of the test compound formulated inan emulsifiable concentrate as in Formulation Example 2 was diluted withwater, and the dilution was sprayed onto the soil surface by means of asmall hand sprayer at a spray volume of 1,000 liters per hectare. Thetest plants were grown in a greenhouse for 20 days, and the herbicidalactivity and phytotoxicity were examined. The results are shown in Table19.

                  TABLE 19                                                        ______________________________________                                                                           Herbicidal                                                  Phytotoxicity     activity                                   Compound                                                                              Dosage                   Rice  Barnyard-                              No.     (g/ha)   Soybean   Corn  plant grass                                  ______________________________________                                        1       500      1         --    1     9                                      3       500      --        --    1     8                                      4       125      0         0     1     10                                     5       125      0         1     0     9                                      6       125      1         --    1     9                                      7       500      --        1     1     10                                     8       500      0         0     0     7                                      9       500      1         0     1     10                                     10      125      0         0     0     8                                      11      125      0         1     1     9                                      13      500      0         1     0     10                                     17      125      0         1     1     9                                      18      125      0         0     1     7                                      19      500      0         0     1     7                                      20      125      0         1     --    10                                     21      125      0         1     --    9                                      30      500      1         0     0     10                                     31      500      0         --    1     9                                      33      125      0         1     1     9                                      34      500      1         1     1     9                                      35      250      1         1     1     9                                      36      500      1         1     1     9                                      41      125      1         0     1     9                                      46      125      --        1     1     9                                      A       500      1         1     1     6                                      G       500      0         0     0     0                                      H       500      0         0     0     1                                      I       500      0         1     0     2                                      J       500      0         1     0     1                                      ______________________________________                                    

Test Example 9

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of cotton, morningglory and johnsongrass were sowed therein 1 to 2cm depth. A designated amount of the test compound formulated in anemulsifiable concentrate as in Formulation Example 2 was diluted withwater, and the dilution was sprayed onto the soil surface by means of asmall hand sprayer at a spray volume of 1,000 liters per hectare. Thetest plants were grown in a greenhouse for 20 days, and the herbicidalactivity and phytotoxicity were examined. The results are shown in Table20.

                  TABLE 20                                                        ______________________________________                                                           Phyto-    Herbicidal activity                              Compound   Dosage  toxicity  Morning-                                                                             Johnson-                                  No.        (g/ha)  Cotton    glory  grass                                     ______________________________________                                        3          500     0         --     8                                         4          500     0         10     9                                         5          500     1         10     9                                         6          500     0         9      10                                        7          500     1         10     7                                         9          500     0         10     7                                         10         500     0         7      9                                         11         500     0         9      10                                        12         500     1         --     7                                         13         500     0         --     8                                         14         500     0         7      --                                        17         500     1         7      10                                        18         500     0         --     10                                        20         500     0         10     10                                        21         500     0         7      9                                         23         500     0         --     9                                         25         500     1         10     7                                         26         500     1         10     9                                         29         500     0         7      9                                         33         500     1         8      9                                         46         500     0         7      7                                         48         500     1         10     10                                        49         500     1         8      10                                        52         500     0         8      10                                        53         500     0         10     10                                                   125     0         10     8                                         54         500     1         10     10                                                   125     0         10     9                                         55         500     1         10     10                                                   125     0         7      8                                         62         500     0         7      8                                         63         500     1         10     10                                                   125     0         10     10                                        64         500     0         10     10                                        A          500     0         0      0                                         G          500     0         0      0                                         H          500     0         1      1                                         I          500     1         3      3                                         J          500     0         0      0                                         ______________________________________                                    

Test Example 10

Wagner's pots (1/5000 are) were filled with paddy field soil, and theseeds of barnyardgrass (Echinochloa oryzicola), broad-leaved weeds (i.e.common falsepimpernel, indian toothcup, waterwort) and hardstem bulrushwere sowed in 1 to 2 cm depth. Water was poured therein to make aflooded condition, and rice seedling of 3-leaf stage were transplantedtherein, and the test plants were grown in a greenhouse. Five days (atthat time barnyardgrass began to germinate) thereafter, a designatedamount of the test compound formulated in an emulsifiable concentrate asin Formulation Example 2 and diluted with water (10 ml) was applied tothe pots by perfusion. The test plants were grown for an additional 19days in the greenhouse, and the herbicidal activity and phytotoxicitywere examined. The results are shown in Table 21. At the time of thetreatment, the depth of water in the pots was kept at 4 cm and followingtwo days, water was let leak a volume corresponding to a 3 cm depth perday.

                  TABLE 21                                                        ______________________________________                                                       Herbicidal activity                                            Com-          Phyto-             Broad-                                       pound Dosage  toxicity   Barnyard-                                                                             leaved Hardstem                              No.   (g/ha)  Rice plant grass   weed   bulrush                               ______________________________________                                        1     250     0          10      10     10                                          63      0          9       10     9                                     2     250     0          10      10     10                                          63      0          8       10     8                                           16      0          8       8      --                                    3     250     1          10      10     10                                          63      0          9       10     --                                    4     16      1          10      10     9                                     5     63      1          10      10     10                                          16      0          10      9      7                                     6     16      1          10      10     --                                    7     63      1          10      10     10                                          16      0          --      8      10                                    8     250     1          10      10     10                                          63      0          8       10     7                                     9     63      0          7       10     8                                     10    63      1          10      10     7                                     17    16      0          9       8      9                                     19    63      0          8       9      8                                     20    16      0          7       8      --                                    21    63      1          9       10     10                                          16      1          10      10     7                                     22    63      1          10      10     10                                          16      0          10      10     7                                     30    250     1          10      10     10                                          63      0          10      10     8                                     31    250     0          10      10     10                                    33    63      1          10      10     8                                     36    63      1          10      10     --                                    42    250     0          8       10     10                                    46    63      1          10      10     8                                     53    16      0          10      10     7                                     62    63      1          10      9      9                                     A     250     0          7       0      6                                           63      0          0       0      0                                     G     250     0          0       0      0                                     H     250     0          0       0      0                                     ______________________________________                                    

Test Example 11

Wagner's pots (1/5000 are) were filled with paddy field soil, and theseeds of barnyardgrass (Echinochloa oryzicola) and broad-leaved weeds(i.e. common false-pimpernel, indian toothcup, waterwort, Ammanniamultiflora) were sowed in 1 to 2 cm depth. Water was poured therein tomake a flooded condition, and rice seedling of 2-leaf stage weretransplanted therein, and the test plants were grown in a greenhouse.Eleven days (at that time barnyardgrass grows to the 2-leaf stage)thereafter, a designated amount of the test compound formulated in anemulsifiable concentrate as in Formulation Example 2 and diluted withwater (10 ml) was applied to the pots by perfusion. The test plants weregrown for an additional 20 days in the greenhouse, and the herbicidalactivity and phytotoxicity were examined. The results are shown in Table22. At the time of the treatment, the depth of water in the pots waskept at 4 cm and following two days, water was let leak a volumecorresponding to a 3 cm depth per day.

                  TABLE 22                                                        ______________________________________                                        Com-            Phyto-     Herbicidal activity                                pound  Dosage   toxicity   Barnyard-                                                                              Broad-leaved                              No.    (g/ha)   Rice plant grass    weed                                      ______________________________________                                        2      250      0          8        8                                         4      63       1          10       9                                         5      250      1          10       8                                                63       0          9        8                                         6      63       1          9        10                                        17     63       0          10       10                                        18     250      1          10       8                                         20     63       1          9        8                                         21     250      1          10       10                                               63       1          9        10                                        22     250      1          10       10                                               63       0          9        10                                        33     63       0          10       7                                         55     63       1          8        9                                         G      250      0          0        0                                         H      250      0          2        0                                         I      250      1          1        0                                         ______________________________________                                    

Test Example 12

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of rice plant, morningglory, common cocklebur, velvetleaf, blacknightshade, barnyardgrass and green foxtail were sowed therein andcultivated for 18 days in a greenhouse. A designated amount of the testcompound formulated in an emulsifiable concentrate as in FormulationExample 2 was diluted with water, and the dilution was sprayed over thefoliage of the test plants by means of a small hand sprater at a sprayvolume of liters per hecare. The test plants were further grown in thegreenhouse for 18 days, and the herbicidal activity and phytotoxicitywere examined. At the time of the application, the test plants weregenerally at the 1 to 4 leaf stage and in 2 to 12 cm height, althoughthe growing stage of the test plants varied depending on their species.The results are shown in Table 23.

                                      TABLE 23                                    __________________________________________________________________________                     Herbicidal activity                                                                           Black                                                                             Barn-                                    Compound                                                                            Dosage                                                                            Phytotoxicity                                                                        Morning-                                                                           Common                                                                              Velvet-                                                                            night-                                                                            yard-                                                                             Green                                No.   (g/ha)                                                                            Rice plant                                                                           glory                                                                              cocklebur                                                                           leaf shade                                                                             grass                                                                             foxtail                              __________________________________________________________________________    30    2000                                                                              0      9    9     9    9   9   9                                    H     2000                                                                              3      0    0     1    5   4   5                                    __________________________________________________________________________

Test Example 13

vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of cotton, giant foxtail, large crabgrass, fall panicum,shattercane, green foxtail, bermudagrass, slender amaranth, pricklysida, black nightshade, morningglory and field bindweed were sowed in 1to 2 cm depth. A designated amount of the test compound formulated in anemulsifiable concentrate as in Formulation Example 2 was diluted withwater, and the dilution was sprayed onto the soil surface by means of asmall hand sprayer at a spray volume of 230 liters per hectare. The testplants were grown outdoor for 21 days, and the herbicidal activity andphytotoxicity were examined. The results are shown in Table 24.

                                      TABLE 24                                    __________________________________________________________________________                Herbicidal activity                                               Com-    Phyto-                                                                            Giant                                                                             Large         Green              Black     Field              pound                                                                             Dosage                                                                            toxicity                                                                          fox-                                                                              crab-                                                                             Fall Shatter-                                                                           fox-                                                                              Bermuda-                                                                            Slender                                                                            Prickly                                                                           night-                                                                             Morning-                                                                           bind-              No. (g/ha)                                                                            Cotton                                                                            tail                                                                              grass                                                                             panicum                                                                            cane tail                                                                              grass amaranth                                                                           sida                                                                              shade                                                                              glory                                                                              weed               __________________________________________________________________________     4  400 0   10  10  10   10   10  10    10   9   10   10   8                  54  200 0   10  10  10   10   10  10    10   10  10   10   10                 F   400 0   0   0   0    0    0   0     0    0   0    0    0                  __________________________________________________________________________

Test Example 14

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of wheat, persian speedwell and field pansy were sowed therein andcultivated for 31 days in a greenhouse. A designated amount of the testcompound formulated in an emulsifiable concentrate as in FormulationExample 2 was diluted with water, and the dilution was sprayed over thefoliage of the test plants by means of an automatic sprayer at a sprayvolume of 1,000 liters per hectare. The test plants were further grownin the greenhouse for 25 days, and the herbicidal activity andphytotoxicity were examined. At the time of the application, the testplants were generally at the 1 to 4 leaf stage and in 3 to 25 cm height,although the growing stage of the test plants varied depending on theirspecies. The results are shown in Table 25.

                  TABLE 25                                                        ______________________________________                                                          Herbicidal activity                                         Com-             Phyto-     Persian                                           pound    Dosage  toxicity   speed- Field                                      No.      (g/ha)  Wheat      well   pansy                                      ______________________________________                                        54       500     1          10     10                                                  125     1          10     10                                         J        500     1          4      5                                                   125     0          2      4                                          ______________________________________                                    

Test Example 15

Containers (40 cm×35 cm bed) were filled with upland field soil, and theseeds of soybean, yellow foxtail, johnsongrass, southern crabgrass,giant foxtail, velvetleaf, slender amaranth, black nightshade andjimsonweed were sowed in 1 to 3 cm depth. A designated amount of thetest compound formulated in an emulsifiable concentrate as inFormulation Example 2 was diluted with-water, and the dilution wassprayed onto the soil surface by means of a small hand sprayer at aspray volume of 430 liters per hectare. The test plants were grownoutdoor for 52 days, and the herbicidal activity and phytotoxicity wereexamined. The results are shown in Table 26.

                                      TABLE 26                                    __________________________________________________________________________                 Herbicidal activity                                              Com-    Phyto-                                                                             Yellow   Southern                                                                           Giant         Black                                pound                                                                             Dosage                                                                            toxicity                                                                           fox-                                                                              Johnson-                                                                           crab-                                                                              fox-                                                                              Velvet-                                                                            Slender                                                                            night-                                                                            Jimson-                          No. (g/ha)                                                                            Soybean                                                                            tail                                                                              grass                                                                              grass                                                                              tail                                                                              leaf amaranth                                                                           shade                                                                             weed                             __________________________________________________________________________    54  100 0    10  10   10   10  10   10   10  9                                F   100 0    0   0    0    0   0    0    0   0                                __________________________________________________________________________

What is claimed is:
 1. An iminothiazoline compound of the formula:##STR47## wherein R⁷ is a halogen atom or a halogen-substituted C₁ -C₂alkyl group and R⁸ is a C₁ -C₆ alkyl group, a C₁ -C₆ alkyloxy group, aC₁ -C₆ alkyloxy group substituted with C₁ -C₂ alkyloxy or phenyl, aphenyl group, a phenoxy group or a halogen-subsituted C₁ -C₆ alkylgroup.
 2. The iminothiazoline compound according to claim 1, wherein R⁷is selected from the group consisting of CF₃, CF₃ CF₂, F, Cl, and Br. 3.The iminothiazoline compound according to claim 1, wherein R⁸ isselected from the group consisting of OC₂ H₅, C₂ H₅, OCH₃, CH₃, OCH₂ CH₂CH₃, CH₂ CH₂ CH₃, ##STR48## and CF₃.
 4. The iminothiazoline compoundaccording to claim 3, wherein R⁷ is selected from the group consistingof CF₃, CF₃ CF₂, F, Cl, and Br.
 5. The iminothiazoline compoundaccording to claim 1, wherein R⁷ is CF₃.
 6. The iminothiazoline compoundaccording to claim 5, wherein R⁸ is a C₁ -C₆ alkyloxy group, a phenylgroup, or a phenoxy group.